Voltammetric analysis of pesticides and their degradation: A case study of Amitraz and its degradants
- Authors: Brimecombe, Rory Dennis
- Date: 2006
- Subjects: Hydrolysis , Biodegradation , Voltammetry , Pesticides -- Biodegradation , Pesticides -- Environmental aspects , Acaricides , Acaricides -- Physiological effect
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4131 , http://hdl.handle.net/10962/d1015724
- Description: Amitraz is a formamide acaricide used predominantly in the control of ectoparasites in livestock and honeybees. Amitraz hydrolysis is rapid and occurs under acidic conditions, exposure to sunlight and biodegradation by microorganisms. The main hydrolysis product of amitraz, 2,4-dimethylaniline, is recalcitrant in the environment and toxic to humans. An electrochemical method for the determination of total amitraz residues and its final breakdown product, 2,4-dimethylaniline, in spent cattle dip, is presented. Cyclic voltammetry at a glassy carbon electrode showed the irreversible oxidation of amitraz and 2,4-dimethylaniline. A limit of detection in the range of 8.5 x 10⁻⁸ M for amitraz and 2 x 10⁻⁸ M for 2,4-dimethylaniline was determined using differential pulse voltammetry. Feasibility studies in which the effect of supporting electrolyte type and pH had on electroanalysis of amitraz and its degradants, showed that pH affects current response as well as the potential at which amitraz and its degradants are oxidised. Britton-Robinson buffer was found to be the most suitable supporting electrolyte for detection of amitraz and its degradants in terms of sensitivity and reproducibility. Studies performed using environmental samples showed that the sensitivity and reproducibility of amitraz and 2,4-dimethylaniline analyses in spent cattle dip were comparable to analyses of amitraz and 2,4-dimethylaniline performed in Britton-Robinson buffer. In addition, the feasibility qf measuring amitraz and 2,4-dimethylaniline in environmental samples was assessed and compared to amitraz and 2,4-dimethylaniline analyses in Britton-Robinson buffer. Amitraz and 2,4-dimethylaniline were readily detectable in milk and honey. Furthermore, it was elucidated that 2,4-dimethylaniline can be metabolised to 3-methylcatechol by Pseudomonas species and the proposed breakdown pathway is presented. The biological degradation of amitraz and subsequent formation of 2,4-dimethylaniline was readily monitored in spent cattle dip. The breakdown of amitraz to 2,4-dimethylaniline and then to 3-MC was monitored using cyclic voltammetry.
- Full Text:
- Date Issued: 2006
- Authors: Brimecombe, Rory Dennis
- Date: 2006
- Subjects: Hydrolysis , Biodegradation , Voltammetry , Pesticides -- Biodegradation , Pesticides -- Environmental aspects , Acaricides , Acaricides -- Physiological effect
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4131 , http://hdl.handle.net/10962/d1015724
- Description: Amitraz is a formamide acaricide used predominantly in the control of ectoparasites in livestock and honeybees. Amitraz hydrolysis is rapid and occurs under acidic conditions, exposure to sunlight and biodegradation by microorganisms. The main hydrolysis product of amitraz, 2,4-dimethylaniline, is recalcitrant in the environment and toxic to humans. An electrochemical method for the determination of total amitraz residues and its final breakdown product, 2,4-dimethylaniline, in spent cattle dip, is presented. Cyclic voltammetry at a glassy carbon electrode showed the irreversible oxidation of amitraz and 2,4-dimethylaniline. A limit of detection in the range of 8.5 x 10⁻⁸ M for amitraz and 2 x 10⁻⁸ M for 2,4-dimethylaniline was determined using differential pulse voltammetry. Feasibility studies in which the effect of supporting electrolyte type and pH had on electroanalysis of amitraz and its degradants, showed that pH affects current response as well as the potential at which amitraz and its degradants are oxidised. Britton-Robinson buffer was found to be the most suitable supporting electrolyte for detection of amitraz and its degradants in terms of sensitivity and reproducibility. Studies performed using environmental samples showed that the sensitivity and reproducibility of amitraz and 2,4-dimethylaniline analyses in spent cattle dip were comparable to analyses of amitraz and 2,4-dimethylaniline performed in Britton-Robinson buffer. In addition, the feasibility qf measuring amitraz and 2,4-dimethylaniline in environmental samples was assessed and compared to amitraz and 2,4-dimethylaniline analyses in Britton-Robinson buffer. Amitraz and 2,4-dimethylaniline were readily detectable in milk and honey. Furthermore, it was elucidated that 2,4-dimethylaniline can be metabolised to 3-methylcatechol by Pseudomonas species and the proposed breakdown pathway is presented. The biological degradation of amitraz and subsequent formation of 2,4-dimethylaniline was readily monitored in spent cattle dip. The breakdown of amitraz to 2,4-dimethylaniline and then to 3-MC was monitored using cyclic voltammetry.
- Full Text:
- Date Issued: 2006
The effect of mussel bed structure on the associated infauna in South Africa and the interaction between mussel and epibiotic barnacles
- Jordaan, Tembisa Nomathamsanqa
- Authors: Jordaan, Tembisa Nomathamsanqa
- Date: 2011
- Subjects: Mytilidae -- South Africa , Mytilus galloprovincialis -- South Africa , Mussel culture -- South Africa , Shellfish culture -- South Africa , Perna -- South Africa , Barnacles -- South Africa , Mussels -- South Africa , Mussels -- Ecology , Barnacles -- Ecology
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5675 , http://hdl.handle.net/10962/d1005360 , Mytilidae -- South Africa , Mytilus galloprovincialis -- South Africa , Mussel culture -- South Africa , Shellfish culture -- South Africa , Perna -- South Africa , Barnacles -- South Africa , Mussels -- South Africa , Mussels -- Ecology , Barnacles -- Ecology
- Description: Mussels are important ecological engineers on intertidal rocks where they create habitat that contributes substantially to overall biodiversity. They provide secondary substratum for other free-living, infaunal or epifaunal organisms, and increase the surface area for settlement by densely packing together into complex multilayered beds. The introduction of the alien invasive mussel Mytilus galloprovincialis has extended the upper limit of mussels on the south coast of South Africa, potentially increasing habitat for associated fauna. The aim of this study was to describe the structure of mussel beds, the general biodiversity associated with multi- and monolayered mussel beds of indigenous Perna perna and alien M. galloprovincialis, and to determine the relationship between mussels and epibiotic barnacles. This was done to determine the community structure of associated macrofauna and the role of mussels as biological facilitators. Samples were collected in Plettenberg Bay, South Africa, where M. galloprovincialis dominates the high mussel zone and P. perna the low zone. Three 15 X 15 cm quadrats were scraped off the rock in the high and low zones, and in the mid zone where the two mussel species co-exist. The samples were collected on 3 occasions. In the laboratory mussel-size was measured and sediment trapped within the samples was separated through 75 μm, 1 mm and 5 mm mesh. The macrofauna was sorted from the 1 mm and 5 mm sieves and identified to species level where possible. The epibiotic relationship between mussels and barnacles was assessed by measuring the prevalence and intensity of barnacle infestation and the condition index of infested mussels. Multivariate analysis was used on the mean abundance data of the species for each treatment (Hierarchical clustering, multidimensional scaling, analysis of similarity and similarity of percentages) and ANOVA was used for most of the statistical analyses. Overall, the results showed that tidal height influences the species composition and abundance of associated fauna. While mussel bed layering influenced the accumulation of sediments; it had no significant effect on the associated fauna. Time of collection also had a strong effect. While there was an overlap of species among samples from January, May and March, the principal species contributing to similarity among the March samples were not found in the other two months. The outcomes of this study showed that low shore mussel beds not only supported a higher abundance and diversity of species, but were also the most structurally complex. Although the condition index of mussels did not correlate to the percentage cover of barnacle epibionts, it was also evident that low shore mussels had the highest prevalence. The levels of barnacle infestation (intensity) for each mussel species were highest where it was common and lowest where it was least abundant. This is viewed as a natural artefact of the distribution patterns of P. perna and M. galloprovincialis across the shore. Mussels are more efficient as facilitators on the low mussel zone than the high mussel zone possibly because they provide habitats that are more effective in protecting the associated macrofauna from the effects of competition and predation, than they are at eliminating the effects of physical stress on the high shore. Although mussels create less stressful habitats and protect organisms from the physical stress of the high shore, there are clear limitations in their ability to provide ideal habitats. The biological associations in an ecosystem can be made weak or strong depending on the external abiotic factors and the adaptability of the affected organisms.
- Full Text:
- Date Issued: 2011
- Authors: Jordaan, Tembisa Nomathamsanqa
- Date: 2011
- Subjects: Mytilidae -- South Africa , Mytilus galloprovincialis -- South Africa , Mussel culture -- South Africa , Shellfish culture -- South Africa , Perna -- South Africa , Barnacles -- South Africa , Mussels -- South Africa , Mussels -- Ecology , Barnacles -- Ecology
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5675 , http://hdl.handle.net/10962/d1005360 , Mytilidae -- South Africa , Mytilus galloprovincialis -- South Africa , Mussel culture -- South Africa , Shellfish culture -- South Africa , Perna -- South Africa , Barnacles -- South Africa , Mussels -- South Africa , Mussels -- Ecology , Barnacles -- Ecology
- Description: Mussels are important ecological engineers on intertidal rocks where they create habitat that contributes substantially to overall biodiversity. They provide secondary substratum for other free-living, infaunal or epifaunal organisms, and increase the surface area for settlement by densely packing together into complex multilayered beds. The introduction of the alien invasive mussel Mytilus galloprovincialis has extended the upper limit of mussels on the south coast of South Africa, potentially increasing habitat for associated fauna. The aim of this study was to describe the structure of mussel beds, the general biodiversity associated with multi- and monolayered mussel beds of indigenous Perna perna and alien M. galloprovincialis, and to determine the relationship between mussels and epibiotic barnacles. This was done to determine the community structure of associated macrofauna and the role of mussels as biological facilitators. Samples were collected in Plettenberg Bay, South Africa, where M. galloprovincialis dominates the high mussel zone and P. perna the low zone. Three 15 X 15 cm quadrats were scraped off the rock in the high and low zones, and in the mid zone where the two mussel species co-exist. The samples were collected on 3 occasions. In the laboratory mussel-size was measured and sediment trapped within the samples was separated through 75 μm, 1 mm and 5 mm mesh. The macrofauna was sorted from the 1 mm and 5 mm sieves and identified to species level where possible. The epibiotic relationship between mussels and barnacles was assessed by measuring the prevalence and intensity of barnacle infestation and the condition index of infested mussels. Multivariate analysis was used on the mean abundance data of the species for each treatment (Hierarchical clustering, multidimensional scaling, analysis of similarity and similarity of percentages) and ANOVA was used for most of the statistical analyses. Overall, the results showed that tidal height influences the species composition and abundance of associated fauna. While mussel bed layering influenced the accumulation of sediments; it had no significant effect on the associated fauna. Time of collection also had a strong effect. While there was an overlap of species among samples from January, May and March, the principal species contributing to similarity among the March samples were not found in the other two months. The outcomes of this study showed that low shore mussel beds not only supported a higher abundance and diversity of species, but were also the most structurally complex. Although the condition index of mussels did not correlate to the percentage cover of barnacle epibionts, it was also evident that low shore mussels had the highest prevalence. The levels of barnacle infestation (intensity) for each mussel species were highest where it was common and lowest where it was least abundant. This is viewed as a natural artefact of the distribution patterns of P. perna and M. galloprovincialis across the shore. Mussels are more efficient as facilitators on the low mussel zone than the high mussel zone possibly because they provide habitats that are more effective in protecting the associated macrofauna from the effects of competition and predation, than they are at eliminating the effects of physical stress on the high shore. Although mussels create less stressful habitats and protect organisms from the physical stress of the high shore, there are clear limitations in their ability to provide ideal habitats. The biological associations in an ecosystem can be made weak or strong depending on the external abiotic factors and the adaptability of the affected organisms.
- Full Text:
- Date Issued: 2011
An analysis of malware evasion techniques against modern AV engines
- Authors: Haffejee, Jameel
- Date: 2015
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:20979 , http://hdl.handle.net/10962/5821
- Description: This research empirically tested the response of antivirus applications to binaries that use virus-like evasion techniques. In order to achieve this, a number of binaries are processed using a number of evasion methods and are then deployed against several antivirus engines. The research also documents the process of setting up an environment for testing antivirus engines, including building the evasion techniques used in the tests. The results of the empirical tests illustrate that an attacker can evade multiple antivirus engines without much effort using well-known evasion techniques. Furthermore, some antivirus engines may respond to the occurrence of an evasion technique instead of the presence of any malicious code. In practical terms, this shows that while antivirus applications are useful for protecting against known threats, their effectiveness against unknown or modified threats is limited.
- Full Text:
- Date Issued: 2015
- Authors: Haffejee, Jameel
- Date: 2015
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:20979 , http://hdl.handle.net/10962/5821
- Description: This research empirically tested the response of antivirus applications to binaries that use virus-like evasion techniques. In order to achieve this, a number of binaries are processed using a number of evasion methods and are then deployed against several antivirus engines. The research also documents the process of setting up an environment for testing antivirus engines, including building the evasion techniques used in the tests. The results of the empirical tests illustrate that an attacker can evade multiple antivirus engines without much effort using well-known evasion techniques. Furthermore, some antivirus engines may respond to the occurrence of an evasion technique instead of the presence of any malicious code. In practical terms, this shows that while antivirus applications are useful for protecting against known threats, their effectiveness against unknown or modified threats is limited.
- Full Text:
- Date Issued: 2015
Evaluation of physiochemical qualities and heavy metal levels of the final effluents of some wastewater treatment facilities in the Eastern Cape Province of South Africa
- Authors: Kulati, Thanduxolo Cullinan
- Date: 2016
- Subjects: Water -- Purification Sewage -- Purification
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/1547 , vital:27417
- Description: Water is the most abundant substance in nature and vital for life activities. The major water sources for use are surface water bodies such as rivers and lakes, and underground aquifers and pore spaces down the water table (Ring, 2003). Water derived from these sources is not necessarily pure since it contains dissolved inorganic and organic substances, living organisms (viruses, bacteria, etc). For these reasons, water intended for domestic uses should be free from toxic substances and microorganisms that are of health significance (WHO, 2005). The availability and quality of water always have played an important role in determining the quality of life. Water quality is closely linked to water use and to the state of economic development (Chennakrishnan et al., 2008). Ground and surface waters can be contaminated by several sources. In urban areas, the careless disposal of industrial effluents and other wastes may contribute greatly to the poor quality of water (Mathuthu et al., 1997). In most developing countries, most areas are located on the watersheds which are the end points of effluents discharged from various industries (Oberholster and Ashton, 2008). South Africa, as a developing country, is experiencing rapid demographic changes due to urbanization, industrialization and population growth. The country has also been identified as being water-scarce, which can lead to a challenge of meeting the increasing water demand due to industrialization and urbanization. Such population growth increase may result in an increase in wastewater output, especially around urban areas.
- Full Text:
- Date Issued: 2016
- Authors: Kulati, Thanduxolo Cullinan
- Date: 2016
- Subjects: Water -- Purification Sewage -- Purification
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/1547 , vital:27417
- Description: Water is the most abundant substance in nature and vital for life activities. The major water sources for use are surface water bodies such as rivers and lakes, and underground aquifers and pore spaces down the water table (Ring, 2003). Water derived from these sources is not necessarily pure since it contains dissolved inorganic and organic substances, living organisms (viruses, bacteria, etc). For these reasons, water intended for domestic uses should be free from toxic substances and microorganisms that are of health significance (WHO, 2005). The availability and quality of water always have played an important role in determining the quality of life. Water quality is closely linked to water use and to the state of economic development (Chennakrishnan et al., 2008). Ground and surface waters can be contaminated by several sources. In urban areas, the careless disposal of industrial effluents and other wastes may contribute greatly to the poor quality of water (Mathuthu et al., 1997). In most developing countries, most areas are located on the watersheds which are the end points of effluents discharged from various industries (Oberholster and Ashton, 2008). South Africa, as a developing country, is experiencing rapid demographic changes due to urbanization, industrialization and population growth. The country has also been identified as being water-scarce, which can lead to a challenge of meeting the increasing water demand due to industrialization and urbanization. Such population growth increase may result in an increase in wastewater output, especially around urban areas.
- Full Text:
- Date Issued: 2016
Geology, regional diamond exploration and diamond provenance of the proterozoic diamondiferous Umkondo conglomerates, Umkondo group, eastern Zimbabwe
- Authors: Zhou, Takawira
- Date: 2016
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/3598 , vital:20528
- Description: The Umkondo Sedimentary Basin in eastern Zimbabwe has been studied by various individuals and organizations since 1901. Their interest had been in finding limestone and beryl and base metal deposits, especially copper, iron and uranium, but these occurrences had proved to be of no economic value (Watson, 1969). The recent discovery of placer diamonds within the Proterozoic basal conglomerates of the Umkondo Sedimentary Basin has now attracted worldwide interest in the basin’s diamond economic potential, in understanding of the geology, and the diamond provenance of the Umkondo conglomerates. The Umkondo Sedimentary Basin basal conglomerate placer deposit might narrowly be defined as a mega-placer because of its sheer large size and high grades, especially on the 70,000 hectare western margin diamond dispersion halo where alluvial diamonds are being mined. Bluck, et al., (2005, pp 213) defines a diamond mega-placer as: . . . a number of linked deposits that are a result of one or a continuous process of transportation and deposition and holds or have held at least >= 50 million carats at >= 95% gem quality, for example, the Orange-Vaal dispersal, off the Kaapvaal craton in South Africa. On craton placers are residual, and transient placers are eroded and deposited into the exit drainage, while terminal placers, the final depositories of diamonds with the highest chances of being mega-placers are deposited into terminal basins like oceans and foreland basins. Though data is limited at the moment, the Umkondo conglomerates caratage is likely to run into hundreds of millions of carats, with a diamond gem content of between twenty and twenty-five percent, as is indicated from recent diamond production data. The greater part of the Umkondo diamonds are likely to be lodged beneath the deep gravels of the Middle and Lower Save River basin, because small remnant tilted mountain blocks and inselbergs forming the caps of hills are what remains of the host conglomerate on the western margin of the Umkondo Basin. Areas to be examined in this document will be the geology; the mode of formation of the Umkondo basin and its sedimentary system; the regional kimberlite exploration around the basin; and diamond production in the Marange diamond field, in order to come up with indications of the provenance of the diamonds within the Umkondo conglomerates. The kimberlite clusters in and around the Umkondo sedimentary basin have all proved to be barren or only nominally diamondiferous and that the kimberlites are between 200Ma and 500Ma and thus much younger than the greater than 1.1Ga Umkondo diamondiferous conglomerates. Studies so far undertaken have not managed to point to the origin, or provenance, of the Umkondo or Marange diamonds, which were discovered on the western edge of the Umkondo Basin and in the east of the basin below the Chimanimani Mountains along the Haroni River. This paper is an attempt to clear up some of the misconceptions surrounding the Marange diamond deposit and to raise interest in the urgent rquirement to study and understand the Umkondo Basin and the origin of its diamonds. The only meaningful studies on diamond occurrence and diamond exploration of the basin were undertaken from 1996 to 2006 by Kimberlitic Searches Zimbabwe (Pvt) Ltd, the then Zimbabwe kimberlite exploration arm of De Beers, Zimbabwe, in their quest to find kimberlites, which were thought to be related to the Umkondo alluvial diamond deposit. As will be shown in the following chapters, many of the discovered kimberlites range from very low grade to non-diamondiferous, and are much younger than the Umkondo conglomerates, whose diamonds are in turn a great deal older. Thus the basic question concerning the origin or provenance of the Umkondo placer diamonds still remains unresolved. Because of the sheer size of the basin, modern, wide-area-coverage, geophysical exploration methods become appropriate to effectively generate diamond potential targets for further examination. This document will attempt to collate various data available to paint a true picture of the state of exploration within the Umkondo Basin.
- Full Text:
- Date Issued: 2016
- Authors: Zhou, Takawira
- Date: 2016
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/3598 , vital:20528
- Description: The Umkondo Sedimentary Basin in eastern Zimbabwe has been studied by various individuals and organizations since 1901. Their interest had been in finding limestone and beryl and base metal deposits, especially copper, iron and uranium, but these occurrences had proved to be of no economic value (Watson, 1969). The recent discovery of placer diamonds within the Proterozoic basal conglomerates of the Umkondo Sedimentary Basin has now attracted worldwide interest in the basin’s diamond economic potential, in understanding of the geology, and the diamond provenance of the Umkondo conglomerates. The Umkondo Sedimentary Basin basal conglomerate placer deposit might narrowly be defined as a mega-placer because of its sheer large size and high grades, especially on the 70,000 hectare western margin diamond dispersion halo where alluvial diamonds are being mined. Bluck, et al., (2005, pp 213) defines a diamond mega-placer as: . . . a number of linked deposits that are a result of one or a continuous process of transportation and deposition and holds or have held at least >= 50 million carats at >= 95% gem quality, for example, the Orange-Vaal dispersal, off the Kaapvaal craton in South Africa. On craton placers are residual, and transient placers are eroded and deposited into the exit drainage, while terminal placers, the final depositories of diamonds with the highest chances of being mega-placers are deposited into terminal basins like oceans and foreland basins. Though data is limited at the moment, the Umkondo conglomerates caratage is likely to run into hundreds of millions of carats, with a diamond gem content of between twenty and twenty-five percent, as is indicated from recent diamond production data. The greater part of the Umkondo diamonds are likely to be lodged beneath the deep gravels of the Middle and Lower Save River basin, because small remnant tilted mountain blocks and inselbergs forming the caps of hills are what remains of the host conglomerate on the western margin of the Umkondo Basin. Areas to be examined in this document will be the geology; the mode of formation of the Umkondo basin and its sedimentary system; the regional kimberlite exploration around the basin; and diamond production in the Marange diamond field, in order to come up with indications of the provenance of the diamonds within the Umkondo conglomerates. The kimberlite clusters in and around the Umkondo sedimentary basin have all proved to be barren or only nominally diamondiferous and that the kimberlites are between 200Ma and 500Ma and thus much younger than the greater than 1.1Ga Umkondo diamondiferous conglomerates. Studies so far undertaken have not managed to point to the origin, or provenance, of the Umkondo or Marange diamonds, which were discovered on the western edge of the Umkondo Basin and in the east of the basin below the Chimanimani Mountains along the Haroni River. This paper is an attempt to clear up some of the misconceptions surrounding the Marange diamond deposit and to raise interest in the urgent rquirement to study and understand the Umkondo Basin and the origin of its diamonds. The only meaningful studies on diamond occurrence and diamond exploration of the basin were undertaken from 1996 to 2006 by Kimberlitic Searches Zimbabwe (Pvt) Ltd, the then Zimbabwe kimberlite exploration arm of De Beers, Zimbabwe, in their quest to find kimberlites, which were thought to be related to the Umkondo alluvial diamond deposit. As will be shown in the following chapters, many of the discovered kimberlites range from very low grade to non-diamondiferous, and are much younger than the Umkondo conglomerates, whose diamonds are in turn a great deal older. Thus the basic question concerning the origin or provenance of the Umkondo placer diamonds still remains unresolved. Because of the sheer size of the basin, modern, wide-area-coverage, geophysical exploration methods become appropriate to effectively generate diamond potential targets for further examination. This document will attempt to collate various data available to paint a true picture of the state of exploration within the Umkondo Basin.
- Full Text:
- Date Issued: 2016
Nonlinear optical properties of Sn(IV) phthalocyanines: experimental and theoretical approach
- Authors: Louzada, Marcel Severiano
- Date: 2017
- Subjects: Phthalocyanines , Nonlinear optics
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/57852 , vital:26996
- Description: This work presents the nonlinear properties of six Sn(IV) Phthalocyanines. Three of the phthalocyanines are linked by an alkylthiol substituent and the rest are linked with a phenoxy substituent. For all six compounds non-linear optic analysis was carried out in four solvents: chloroform, toluene, dichloromethane, and tetrahydrofuran, and their differences were recorded. Calculation of the linear, singlet excited, triplet excited and two photon absorption cross-sections were also carried out and the results compared. To form a comparison the first order hyperpolarizabilities, DFT calculations were also performed and the results compared to see if the behaviour between the two properties can be predicted using DFT.
- Full Text:
- Date Issued: 2017
- Authors: Louzada, Marcel Severiano
- Date: 2017
- Subjects: Phthalocyanines , Nonlinear optics
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/57852 , vital:26996
- Description: This work presents the nonlinear properties of six Sn(IV) Phthalocyanines. Three of the phthalocyanines are linked by an alkylthiol substituent and the rest are linked with a phenoxy substituent. For all six compounds non-linear optic analysis was carried out in four solvents: chloroform, toluene, dichloromethane, and tetrahydrofuran, and their differences were recorded. Calculation of the linear, singlet excited, triplet excited and two photon absorption cross-sections were also carried out and the results compared. To form a comparison the first order hyperpolarizabilities, DFT calculations were also performed and the results compared to see if the behaviour between the two properties can be predicted using DFT.
- Full Text:
- Date Issued: 2017
Template-assisted sol-gel synthesis of carbon doped titanium dioxide nanotubes and their characterization
- Authors: Takata, Nwabisa
- Date: 2017
- Subjects: Nanotechnology Titanium dioxide Nanostructures
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/13194 , vital:39473
- Description: This study reveals the effects of doping on the morphological, structural and optical properties of titanium dioxide (TiO2) nanotubes (TNTs), synthesized by sol-gel template-assisted sol-gel technique. The nanotubes (TNTs) were prepared in anodic alumina membranes (AAM) with a pore diameter range of 110-210 nm by using titanium tetra butoxide as a sol-gel precursor and oxalic acid dihydrate as a dopant source. The synthesized nanotubes were evaluated using scanning electron microscope (SEM), energy dispersive spectroscopy (EDX), fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), confocal Raman spectroscopy (CRS) and photoluminescence spectroscopy (PL). SEM analysis has revealed the presence of closely-packed TNTs, with a modal external tube diameters of 150, 170, 210,190 and 210 nm for the un-doped TNTs, 9 mM carbon doped-TNTs (C-TNTs), 27 mM C-TNTs, 45 mM C-TNTs and 75 mM C-TNTs respectively. The diameters are consistent with the AAM diameter range. EDX spectra revealed the presence of Ti peaks at 0.45 and 4.9 keV corresponding to Kα1 and Kβ1 emission lines respectively. Oxygen exhibits a signal at 0.5 keV corresponding to Kα1 emission line. The occurrence of these peaks in the EDX spectra endorses the existence of Ti and O atoms in the prepared titanium dioxide nanotubes. FTIR spectroscopy has revealed the presence of vibration modes at 580-660 cm-1 indicating the presence of Ti-O bonds and additional vibration modes at 2324 cm-1 resulting from C-O stretching in the C-TNTs. The XRD analysis has revealed the presence of a mixed anatase-brookite phase with diffraction peaks at 2θ angles of 25.49⁰, 38.11⁰, 40.60º, 48.14⁰, 54.58⁰, 63.00⁰, 70.11⁰ and 75.66⁰. Additionally, XRD analysis has revealed elongation of lattice parameter “c” from 9.143 to 9.830 Å with carbon concentration increase. Lattice expansion indicates the possibility of carbon substituting oxygen sites. Raman large area scan has revealed the presence of rutile, brookite and anatase for the undoped samples. On doping the rutile phase of TiO2 has shown to be suppressed by the presence of carbon atoms such that the doped samples consist of brookite and anatase phases only. The Eg1 mode of anatase of the undoped TNTs at 153. 78 cm-1 was red shifted by Δ9.78 cm-1 relative to the bulk anatase TiO2. This was attributed to decrease in particle size, presence of brookite and phonon confinement. Upon doping, the 9 mM C-TNTs, 27 mM TNTs and 75 mM TNTs have shown a red shift of Δ0. 09 cm-1, Δ1. 39 cm-1 and 1.81 cm-1 respectively, suggesting the incorporation of carbon in the TiO2 matrix. CRS depth profiling in the XZ direction has also validated the presence of a mixed anatase-brookite phase at Raman active modes 153.19 cm-1, 208.87 cm-1, 404.55 cm-1, 523.26 cm-1 and 648.55 cm-1. Photoluminescence spectra of carbon doped TiO2 showed two emission peaks at 398 nm attributed to annihilation of excitons while the broad peak at 400-460 nm was attributed to the presence of oxygen vacancies. The peak intensity of the 45 mM C-TNTs has shown a lower PL intensity suggesting that efficiency of charge separation was higher and recombination rate was lower than other carbon containing samples.
- Full Text:
- Date Issued: 2017
- Authors: Takata, Nwabisa
- Date: 2017
- Subjects: Nanotechnology Titanium dioxide Nanostructures
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/13194 , vital:39473
- Description: This study reveals the effects of doping on the morphological, structural and optical properties of titanium dioxide (TiO2) nanotubes (TNTs), synthesized by sol-gel template-assisted sol-gel technique. The nanotubes (TNTs) were prepared in anodic alumina membranes (AAM) with a pore diameter range of 110-210 nm by using titanium tetra butoxide as a sol-gel precursor and oxalic acid dihydrate as a dopant source. The synthesized nanotubes were evaluated using scanning electron microscope (SEM), energy dispersive spectroscopy (EDX), fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), confocal Raman spectroscopy (CRS) and photoluminescence spectroscopy (PL). SEM analysis has revealed the presence of closely-packed TNTs, with a modal external tube diameters of 150, 170, 210,190 and 210 nm for the un-doped TNTs, 9 mM carbon doped-TNTs (C-TNTs), 27 mM C-TNTs, 45 mM C-TNTs and 75 mM C-TNTs respectively. The diameters are consistent with the AAM diameter range. EDX spectra revealed the presence of Ti peaks at 0.45 and 4.9 keV corresponding to Kα1 and Kβ1 emission lines respectively. Oxygen exhibits a signal at 0.5 keV corresponding to Kα1 emission line. The occurrence of these peaks in the EDX spectra endorses the existence of Ti and O atoms in the prepared titanium dioxide nanotubes. FTIR spectroscopy has revealed the presence of vibration modes at 580-660 cm-1 indicating the presence of Ti-O bonds and additional vibration modes at 2324 cm-1 resulting from C-O stretching in the C-TNTs. The XRD analysis has revealed the presence of a mixed anatase-brookite phase with diffraction peaks at 2θ angles of 25.49⁰, 38.11⁰, 40.60º, 48.14⁰, 54.58⁰, 63.00⁰, 70.11⁰ and 75.66⁰. Additionally, XRD analysis has revealed elongation of lattice parameter “c” from 9.143 to 9.830 Å with carbon concentration increase. Lattice expansion indicates the possibility of carbon substituting oxygen sites. Raman large area scan has revealed the presence of rutile, brookite and anatase for the undoped samples. On doping the rutile phase of TiO2 has shown to be suppressed by the presence of carbon atoms such that the doped samples consist of brookite and anatase phases only. The Eg1 mode of anatase of the undoped TNTs at 153. 78 cm-1 was red shifted by Δ9.78 cm-1 relative to the bulk anatase TiO2. This was attributed to decrease in particle size, presence of brookite and phonon confinement. Upon doping, the 9 mM C-TNTs, 27 mM TNTs and 75 mM TNTs have shown a red shift of Δ0. 09 cm-1, Δ1. 39 cm-1 and 1.81 cm-1 respectively, suggesting the incorporation of carbon in the TiO2 matrix. CRS depth profiling in the XZ direction has also validated the presence of a mixed anatase-brookite phase at Raman active modes 153.19 cm-1, 208.87 cm-1, 404.55 cm-1, 523.26 cm-1 and 648.55 cm-1. Photoluminescence spectra of carbon doped TiO2 showed two emission peaks at 398 nm attributed to annihilation of excitons while the broad peak at 400-460 nm was attributed to the presence of oxygen vacancies. The peak intensity of the 45 mM C-TNTs has shown a lower PL intensity suggesting that efficiency of charge separation was higher and recombination rate was lower than other carbon containing samples.
- Full Text:
- Date Issued: 2017
The potential of hydrellia egeriae rodrigues (diptera: ephydridae) as a biocontrol agent for egeria densa planch. (hydrocharitaceae) in South Africa
- Authors: Smith, Rosali
- Date: 2017
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/53733 , vital:26314
- Description: The integrity of South Africa’s valuable freshwater ecosystems has been threatened by aquatic invasive plants since the 1900s. Floating aquatic weeds, such as Eichhornia crassipes (C. Mart) Solms (Pondederiaceae), Pistia stratiotes L. (Araceae), Salvinia molesta D.S. Mitchell (Salviniaceae), Azolla filiculoides Lam. (Azollaceae), and the emergent weed, Myriophyllum aquaticum Verdc. (Haloragaceae) benefited from open, nutrient-rich water bodies. Due to the limitations of mechanical and chemical control in aquatic environments, classical biological control has been a huge asset in managing these weeds; consequently bringing them under complete or substantial control. However, submerged aquatic weeds are widely distributed through the aquarium trade in South Africa; facilitating their invasion into new habitats. The removal of surface mats following the successful management of floating weeds has enhanced the growth and competitive ability of submerged aquatic weeds, such as Hydrilla verticillata (L.f.) Royle (Hydrocharitaceae), Myriophyllum spicatum L. (Haloragaceae) and Egeria densa Planch. (Hydrocharitaceae) in South Africa. Of these species, E. densa has become the most widely distributed, invading numerous systems across South Africa. Compared to other exotic submerged aquatic plants, E. densa is the only species capable of inhabiting freshwater systems in every province and therefore, it is vital to manage existing populations and prevent its further distribution and invasion. Hydrellia spp. (Diptera: Ephydridae) biological control agents have been used extensively in the management of submerged aquatic weeds elsewhere, particularly those in the Hydrocharitaceae (Balciunas and Burrows 1996; Wheeler and Center 2001. Hydrellia egeriae Rodrigues (Diptera: Ephydridae) has been identified as a promising candidate for E. densa and was imported into quarantine at Rhodes University, Grahamstown in 2014. The aims of this study were to conduct a pre-release assessment of the potential of H. egeriae as a biological control agent for E. densa in South Africa. The first objective of this study was to establish the life history of the agent under controlled conditions on E. densa found in South Africa, as well as its population growth parameters to predict its invasion success in the field. Secondly, laboratory host-specificity testing was conducted to validate the host range of the agent, in view of published native range host-specificity testing, and to establish potential risks to non-target species, should it be released. Finally, a biological control agent should also effectively reduce the fitness of its host plant, and therefore, impact studies were conducted. Laboratory impact studies have been limited in the past, in that they only investigate agent damage for short ecological periods, thus underestimating the damage capacity of the agent under investigation. Therefore, the damage capacity of H. egeriae was investigated over three consecutive generations in multi-generational impact trials. In a controlled environment of 22 ± 2°C, H. egeriae exhibited the ability to rapidly increase in population size within a short period of time, which will enhance agent establishment and build-up in the field. Host-specificity trials indicated that H. egeriae has a host range restricted to the Hydrocharitaceae, with exploratory feeding and development on Lagarosiphon major Ridley, L. muscoides Harvey and Vallisneria spiralis L. However, only L. major supported agent development during paired larval choice tests, and continuation trials showed that the test species was not physiologically capable of supporting viable agent populations. Risk analysis illustrated that the feeding and reproductive risks that H. egeriae pose to non-target species are very low and therefore, H. egeriae should be safe for release in South Africa. Additionally, significant damage to vital plant structures (shoot growth and side shoot length) was only recorded under high (five larvae) agent abundances. Encouragingly, the number of leaves mined at the end of the experiment was similar for both intermediate (three) and high (five) larval abundances, suggesting that cumulative leaf-mining under intermediate larval abundances has the potential to reduce the fitness of E. densa, given sufficient time. Results from pre-release assessments provide a robust understanding of the specialization of the potential biological control agent to its host plant. Nevertheless, the absolute success of a biological control programme depends on the many factors after prerelease assessments that determine agent establishment, persistence and target weed suppression, e.g. mass-rearing, release protocols and a/biotic factors within the recipient community. Considering these factors, the best mass-rearing and release protocols are proposed here and future research priorities are identified. Finally, the long term success for managing E. densa in South Africa will require a holistic approach to address the underlying factors, such as eutrophication and human-mediated distribution that drive submerged aquatic plant invasions.
- Full Text:
- Date Issued: 2017
- Authors: Smith, Rosali
- Date: 2017
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/53733 , vital:26314
- Description: The integrity of South Africa’s valuable freshwater ecosystems has been threatened by aquatic invasive plants since the 1900s. Floating aquatic weeds, such as Eichhornia crassipes (C. Mart) Solms (Pondederiaceae), Pistia stratiotes L. (Araceae), Salvinia molesta D.S. Mitchell (Salviniaceae), Azolla filiculoides Lam. (Azollaceae), and the emergent weed, Myriophyllum aquaticum Verdc. (Haloragaceae) benefited from open, nutrient-rich water bodies. Due to the limitations of mechanical and chemical control in aquatic environments, classical biological control has been a huge asset in managing these weeds; consequently bringing them under complete or substantial control. However, submerged aquatic weeds are widely distributed through the aquarium trade in South Africa; facilitating their invasion into new habitats. The removal of surface mats following the successful management of floating weeds has enhanced the growth and competitive ability of submerged aquatic weeds, such as Hydrilla verticillata (L.f.) Royle (Hydrocharitaceae), Myriophyllum spicatum L. (Haloragaceae) and Egeria densa Planch. (Hydrocharitaceae) in South Africa. Of these species, E. densa has become the most widely distributed, invading numerous systems across South Africa. Compared to other exotic submerged aquatic plants, E. densa is the only species capable of inhabiting freshwater systems in every province and therefore, it is vital to manage existing populations and prevent its further distribution and invasion. Hydrellia spp. (Diptera: Ephydridae) biological control agents have been used extensively in the management of submerged aquatic weeds elsewhere, particularly those in the Hydrocharitaceae (Balciunas and Burrows 1996; Wheeler and Center 2001. Hydrellia egeriae Rodrigues (Diptera: Ephydridae) has been identified as a promising candidate for E. densa and was imported into quarantine at Rhodes University, Grahamstown in 2014. The aims of this study were to conduct a pre-release assessment of the potential of H. egeriae as a biological control agent for E. densa in South Africa. The first objective of this study was to establish the life history of the agent under controlled conditions on E. densa found in South Africa, as well as its population growth parameters to predict its invasion success in the field. Secondly, laboratory host-specificity testing was conducted to validate the host range of the agent, in view of published native range host-specificity testing, and to establish potential risks to non-target species, should it be released. Finally, a biological control agent should also effectively reduce the fitness of its host plant, and therefore, impact studies were conducted. Laboratory impact studies have been limited in the past, in that they only investigate agent damage for short ecological periods, thus underestimating the damage capacity of the agent under investigation. Therefore, the damage capacity of H. egeriae was investigated over three consecutive generations in multi-generational impact trials. In a controlled environment of 22 ± 2°C, H. egeriae exhibited the ability to rapidly increase in population size within a short period of time, which will enhance agent establishment and build-up in the field. Host-specificity trials indicated that H. egeriae has a host range restricted to the Hydrocharitaceae, with exploratory feeding and development on Lagarosiphon major Ridley, L. muscoides Harvey and Vallisneria spiralis L. However, only L. major supported agent development during paired larval choice tests, and continuation trials showed that the test species was not physiologically capable of supporting viable agent populations. Risk analysis illustrated that the feeding and reproductive risks that H. egeriae pose to non-target species are very low and therefore, H. egeriae should be safe for release in South Africa. Additionally, significant damage to vital plant structures (shoot growth and side shoot length) was only recorded under high (five larvae) agent abundances. Encouragingly, the number of leaves mined at the end of the experiment was similar for both intermediate (three) and high (five) larval abundances, suggesting that cumulative leaf-mining under intermediate larval abundances has the potential to reduce the fitness of E. densa, given sufficient time. Results from pre-release assessments provide a robust understanding of the specialization of the potential biological control agent to its host plant. Nevertheless, the absolute success of a biological control programme depends on the many factors after prerelease assessments that determine agent establishment, persistence and target weed suppression, e.g. mass-rearing, release protocols and a/biotic factors within the recipient community. Considering these factors, the best mass-rearing and release protocols are proposed here and future research priorities are identified. Finally, the long term success for managing E. densa in South Africa will require a holistic approach to address the underlying factors, such as eutrophication and human-mediated distribution that drive submerged aquatic plant invasions.
- Full Text:
- Date Issued: 2017
Farmers' perceptions of insect pests in the Eastern Cape maize-based cropping systems and the effects of crop residue management on insect pest populations
- Authors: Kadango, Tendayi Lovemore
- Date: 2018
- Subjects: Cropping systems Crop residue management Corn -- Diseases and pests
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/6202 , vital:29507
- Description: Maize (Zea mays L.) is one of the most important crops in South Africa that is cultivated for food, feed and as a cash crop. Maize in the Eastern Cape is typically grown for consumption and the Province is one of the least producers owing to small landholdings, poor production conditions and pests. This study investigated: (i) the different maize cropping systems smallholder farmers practice in the Eastern Cape (EC), (ii) the major maize insect pests within the identified cropping systems, (iii) the perceptions of Eastern Cape smallholder maize farmers on the effects of insect pests, and (iv) the effects of crop residues on insect pests’ population dynamics. Four major cropping systems namely: maize sole cropping without rotations by government sponsored farmers (GCP) (94 percent), maize intercropping without rotations by independent farmers (IF) (79 percent), maize sole cropping without rotations by IF (67 percent) and maize intercropping without rotations by GCP (61 percent) were identified. The choice of a cropping system by the smallholder farmers was significantly influenced by source of sponsorship, the difference in their district localities, tenure system, availability of inputs and farming equipment, percentage of farmland farmers allocate to maize, maize varieties, farming experience, fallow operations and access to irrigation facilities. The major constraints faced by the farmers in maize production are the attack by insect pests, weeds competition, drought, the lack of fencing around the fields and destruction by mammals. The major insect pests identified were stalk borers (Busseola fusca, Chilo partellus), cutworms (Agrotis spp.), aphids (Rhopalosiphum maidis), bollworms (Helicoverpa armigera) and weevils (Sitophylus spp.). The most popular control measures employed were the use of GM maize and pesticides. Results from the field trial showed that field crickets were the major ground dwelling insect pests observed followed by bollworms and cutworms. However, there were no significant influence of residue retention on the insects’ diversity indices, richness, and evenness. Above ground insects sampling revealed the domination by four major insects namely, cutworms, maize stalk borer, bollworms, and spotted stalk borer. Residue management significantly influenced the infestation by spotted stalk borer only on maize plots. However, the general trend was that there was less infestation by the insects in plots where residues were retained than the ones with residue removed. Results from the study indicate that government sponsorship is significantly influencing the maize cropping systems of the smallholder farmers of the Eastern Cape.
- Full Text:
- Date Issued: 2018
- Authors: Kadango, Tendayi Lovemore
- Date: 2018
- Subjects: Cropping systems Crop residue management Corn -- Diseases and pests
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/6202 , vital:29507
- Description: Maize (Zea mays L.) is one of the most important crops in South Africa that is cultivated for food, feed and as a cash crop. Maize in the Eastern Cape is typically grown for consumption and the Province is one of the least producers owing to small landholdings, poor production conditions and pests. This study investigated: (i) the different maize cropping systems smallholder farmers practice in the Eastern Cape (EC), (ii) the major maize insect pests within the identified cropping systems, (iii) the perceptions of Eastern Cape smallholder maize farmers on the effects of insect pests, and (iv) the effects of crop residues on insect pests’ population dynamics. Four major cropping systems namely: maize sole cropping without rotations by government sponsored farmers (GCP) (94 percent), maize intercropping without rotations by independent farmers (IF) (79 percent), maize sole cropping without rotations by IF (67 percent) and maize intercropping without rotations by GCP (61 percent) were identified. The choice of a cropping system by the smallholder farmers was significantly influenced by source of sponsorship, the difference in their district localities, tenure system, availability of inputs and farming equipment, percentage of farmland farmers allocate to maize, maize varieties, farming experience, fallow operations and access to irrigation facilities. The major constraints faced by the farmers in maize production are the attack by insect pests, weeds competition, drought, the lack of fencing around the fields and destruction by mammals. The major insect pests identified were stalk borers (Busseola fusca, Chilo partellus), cutworms (Agrotis spp.), aphids (Rhopalosiphum maidis), bollworms (Helicoverpa armigera) and weevils (Sitophylus spp.). The most popular control measures employed were the use of GM maize and pesticides. Results from the field trial showed that field crickets were the major ground dwelling insect pests observed followed by bollworms and cutworms. However, there were no significant influence of residue retention on the insects’ diversity indices, richness, and evenness. Above ground insects sampling revealed the domination by four major insects namely, cutworms, maize stalk borer, bollworms, and spotted stalk borer. Residue management significantly influenced the infestation by spotted stalk borer only on maize plots. However, the general trend was that there was less infestation by the insects in plots where residues were retained than the ones with residue removed. Results from the study indicate that government sponsorship is significantly influencing the maize cropping systems of the smallholder farmers of the Eastern Cape.
- Full Text:
- Date Issued: 2018
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