Natural resource products contribute to poverty mitigation amongst urbanising communities in sub-saharan Africa
- Shackleton, Charlie M, Schlesinger, Johannes, Kaoma, Humphrey, Davenport, N I, Ward, Catherine D, Evans, Michelle L, Drescher, Axel W
- Authors: Shackleton, Charlie M , Schlesinger, Johannes , Kaoma, Humphrey , Davenport, N I , Ward, Catherine D , Evans, Michelle L , Drescher, Axel W
- Date: 2014
- Language: English
- Type: text
- Identifier: vital:6624 , http://hdl.handle.net/10962/d1016232
- Description: [From Introduction] Urbanisation in sub-Saharan Africa: changing the locus of poverty. Urbanisation is a global phenomenon that is changing the face of the Earth, as well as how people earn a living and secure their livelihoods. In 2006 the number of urban people in the world surpassed the number of rural people, and this gap will continue to grow. In only 16 years (by 2030) just under two-thirds of the world's people will be urban dwellers. Whilst most of the developed world and large parts of Latin America already have more than threequarters of their populations living in cities and towns, most countries in Asia and sub-Saharan Africa are still catching up. This means that they are experiencing massive migrations from rural to urban areas as rural people wish to swap the insecurities of rural living for the allure of secure employment and better services for health, education, sanitation and transport in towns and cities. Sub-Saharan Africa (SSA) is the most rapidly urbanising region of the globe. According to UN-Habitat, in 1990, only 28 % of the region's inhabitants lived in towns and cities; that increased to approximately 32 % in 2001 and 41 % in 2010. The size of the urban population is likely to surpass the rural one around 2025. Contrary to popular belief, most urban residents in SSA (and globally) live in small towns rather than massive megacities; with just over half living in towns of less than 200,000 people and 78 % living in towns of less than 500,000 residents. Only 14 % of urban dwellers live in cities of more than one million people. Many new urban households maintain strong links to relatives and clans in rural areas, with circular migration patterns emerging as the urban transition takes place over several decades. The implications of this extremely rapid urbanisation in SSA countries for livelihoods and poverty are widely debated. UN-Habitat highlights a relatively unique aspect of urbanisation in SSA as being the accompanying high rate of growth in informal settlements or slums. In other words, not all rural migrants to towns and cities find secure incomes or shelter. Some slum areas have become permanent features where inter-generational poverty is reproduced. Although urban areas are producing an increasing share of national wealth in SSA countries, some argue that slowly the nexus of poverty is shifting towards urban areas. Rates of poverty are high in rural areas of SSA, but migration and internal population growth means that in some countries the number of urban poor almost matches the number of rural poor, and it is likely to grow. The informal economy contributes an average of 40 – 45 % of total urban GDP, which is higher than any other region of the world.
- Full Text:
- Authors: Shackleton, Charlie M , Schlesinger, Johannes , Kaoma, Humphrey , Davenport, N I , Ward, Catherine D , Evans, Michelle L , Drescher, Axel W
- Date: 2014
- Language: English
- Type: text
- Identifier: vital:6624 , http://hdl.handle.net/10962/d1016232
- Description: [From Introduction] Urbanisation in sub-Saharan Africa: changing the locus of poverty. Urbanisation is a global phenomenon that is changing the face of the Earth, as well as how people earn a living and secure their livelihoods. In 2006 the number of urban people in the world surpassed the number of rural people, and this gap will continue to grow. In only 16 years (by 2030) just under two-thirds of the world's people will be urban dwellers. Whilst most of the developed world and large parts of Latin America already have more than threequarters of their populations living in cities and towns, most countries in Asia and sub-Saharan Africa are still catching up. This means that they are experiencing massive migrations from rural to urban areas as rural people wish to swap the insecurities of rural living for the allure of secure employment and better services for health, education, sanitation and transport in towns and cities. Sub-Saharan Africa (SSA) is the most rapidly urbanising region of the globe. According to UN-Habitat, in 1990, only 28 % of the region's inhabitants lived in towns and cities; that increased to approximately 32 % in 2001 and 41 % in 2010. The size of the urban population is likely to surpass the rural one around 2025. Contrary to popular belief, most urban residents in SSA (and globally) live in small towns rather than massive megacities; with just over half living in towns of less than 200,000 people and 78 % living in towns of less than 500,000 residents. Only 14 % of urban dwellers live in cities of more than one million people. Many new urban households maintain strong links to relatives and clans in rural areas, with circular migration patterns emerging as the urban transition takes place over several decades. The implications of this extremely rapid urbanisation in SSA countries for livelihoods and poverty are widely debated. UN-Habitat highlights a relatively unique aspect of urbanisation in SSA as being the accompanying high rate of growth in informal settlements or slums. In other words, not all rural migrants to towns and cities find secure incomes or shelter. Some slum areas have become permanent features where inter-generational poverty is reproduced. Although urban areas are producing an increasing share of national wealth in SSA countries, some argue that slowly the nexus of poverty is shifting towards urban areas. Rates of poverty are high in rural areas of SSA, but migration and internal population growth means that in some countries the number of urban poor almost matches the number of rural poor, and it is likely to grow. The informal economy contributes an average of 40 – 45 % of total urban GDP, which is higher than any other region of the world.
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Necrophiliac Narration and the Business of Friends: Damon Galgut’s The Good Doctor
- Authors: Marais, Mike
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/144159 , vital:38316 , DOI: 10.1080/17533171.2014.918406
- Description: Set in the period following South Africa’s first democratic elections, Damon Galgut’s The Good Doctor traces the friendship that develops between two doctors working at a rural hospital. While it does not deal overtly with the politics of the “new” South Africa, the novel’s treatment of friendship, which cuts across the distinction between the private and the public, reflects obliquely on the nature of the emerging democratic dispensation. In this paper, I explore the link that Galgut constructs between friendship and community, and argue that his portrayal of the former points to the possibility of a form of community that is premised on a “common strangeness.”
- Full Text:
- Authors: Marais, Mike
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/144159 , vital:38316 , DOI: 10.1080/17533171.2014.918406
- Description: Set in the period following South Africa’s first democratic elections, Damon Galgut’s The Good Doctor traces the friendship that develops between two doctors working at a rural hospital. While it does not deal overtly with the politics of the “new” South Africa, the novel’s treatment of friendship, which cuts across the distinction between the private and the public, reflects obliquely on the nature of the emerging democratic dispensation. In this paper, I explore the link that Galgut constructs between friendship and community, and argue that his portrayal of the former points to the possibility of a form of community that is premised on a “common strangeness.”
- Full Text:
New geochemical constraints on the genesis of the Gamsberg zinc deposit, Namaqualand Metamorphic Province, South Africa
- Authors: Foulkes, Susan Elizabeth
- Date: 2014
- Subjects: Zinc ores -- South Africa -- Gamsberg , Mines and mineral resources -- South Africa -- Gamsberg , Mineralogy -- South Africa -- Gamsberg , Molecular evolution , Geology -- South Africa -- Namaqualand
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5054 , http://hdl.handle.net/10962/d1012084 , Zinc ores -- South Africa -- Gamsberg , Mines and mineral resources -- South Africa -- Gamsberg , Mineralogy -- South Africa -- Gamsberg , Molecular evolution , Geology -- South Africa -- Namaqualand
- Description: The base metal massive sulfide deposits of the Aggeneys-Gamsberg (A-G) District are hosted within the Mesoproterozoic Bushmanland Group of the Namaqua-Natal Metamorphic Complex in the Northern Cape Province of South Africa. The district displays an apparent eastward trend in the economic concentration of base metals (+ barite) from relatively Cu-Pb-rich, Ba-poor mineralisation at Black Mountain to Zn- and Ba-rich ores at Gamsberg. Base metal sulfides at Gamsberg are restricted to the so called Gams (Iron) Formation which comprises a sulfidic mineralized unit (“B”) enveloped within a sequence of meta-sedimentary units (“A” and “C”). The aim of the study was to shed further light on the genesis and chemical evolution of the sulfide mineralisation at Gamsberg in the context of the entire A-G District, by interrogating further the apparent district-wide trend in base metal distribution. The Gams Iron Formation was sampled and studied from one key drill core intersection (“G1”) which intersects the largest part of it as described elsewhere; a small number of additional samples from a second drill core (“G2”) complemented the main sample suite. Minerals that make up the silicate assemblages across the studied section include quartz, garnet, pyroxene, pyroxenoid, phyllosilicates, carbonates, amphiboles, oxides (chiefly magnetite) and graphite. In a stratigraphic context, the mineralogical variations conform directly to those documented in the relevant literature from the Gamsberg locality. These are coupled, where possible, with mineral-chemical profiles of selected silicate species which replicate those of bulk-rock compositions, particularly with respect to Mn, Fe and Ca in the upper C Unit of the studied section. These signals collectively track the characteristic transition from a terrigenous, siliciclastic sediment-dominated footwall to an exhalative sediment-dominated hanging wall to the sulfide mineralisation as also seen in similar deposits elsewhere, particularly with respect to the characteristic Mn-rich signature increasingly observed in the hanging wall C Unit. The foregoing suggests that the examined section faithfully records the interpreted primary stratigraphy of the deposits, despite the complex structural and metamorphic overprint that characterises the region. This facilitates a stratigraphic analytical approach on the sulfidic Unit B, through a combination of mineral-chemical and stable isotope analyses. Dominant sulfides in Unit B are sphalerite and pyrite, with lesser pyrrhotite and minor galena. Sphalerite shows high and generally invariant contents of Fe (mean 12.18wt%, as FeS) whereas Zn anti-correlates with Mn (mean 5.58wt%, as MnS). Isotopic analyses for S, Fe and Zn in hand-picked sphalerite and pyrite separates were used with a view to providing new evidence for chemical and isotopic variation within the sulfide ore-body in a vertical (i.e. stratigraphic) sense, discuss the implications thereof, and ultimately interpret the new data in light of similar existing data from the A-G District and elsewhere. The δ³⁴S data for pyrite (plus a single pyrrhotite grain) and sphalerite from both cores G1 and G2 show comparable compositional ranges between 22.9 and 30.4‰ and between 27 and 30.1‰ respectively. The δ⁵⁶Fe data for pyrite show a range between -1.85 and 0.19‰, whereas seven sphalerite separates have a very narrow range of δ⁶⁶Zn from 0.06 to 0.20‰. The atypically high sulfur isotope data reported in this study are interpreted to reflect sedimentary deposition of primary sulfide ore at Gamsberg from an isotopically highly evolved seawater sulfate source through large-scale Rayleigh fractionation processes. Thermogenic sulfate reduction is proposed to have been the main reductive mechanism from seawater sulfate to sulfide, given the absence of very low δ³⁴S data for sulfides anywhere in the A-G District. By contrast, the δ⁶⁶Zn values for sphalerite are for all intents and purposes invariant and very close to 0‰, and therefore suggest little Zn isotope fractionation from an original exhalative fluid source. On this evidence alone, Zn isotopes therefore appear to hold little promise as a proxy of the chemical and isotopic evolution of SEDEX deposits in space and time, although this can only be verified through further application in the broader A-G District and similar deposits elsewhere. The apparent decoupling of Zn and S isotopes in the Gamsberg sulfide deposit, however, points towards diverse sources of these two components, i.e. ascending metalliferous brines versus seawater respectively. Finally, pyrite δ⁵⁶Fe data do show a stratigraphic trend of generally declining values up-section, which are interpreted to reflect the influence of broadly coeval precipitation of isotopically heavy Fe-oxides on a broader-scale – now preserved as abundant magnetite through metamorphism. Further work on the iron isotope composition of silicate-and oxide-hosted Fe on a local-to-district scale will assist in testing this interpretation.
- Full Text:
- Authors: Foulkes, Susan Elizabeth
- Date: 2014
- Subjects: Zinc ores -- South Africa -- Gamsberg , Mines and mineral resources -- South Africa -- Gamsberg , Mineralogy -- South Africa -- Gamsberg , Molecular evolution , Geology -- South Africa -- Namaqualand
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5054 , http://hdl.handle.net/10962/d1012084 , Zinc ores -- South Africa -- Gamsberg , Mines and mineral resources -- South Africa -- Gamsberg , Mineralogy -- South Africa -- Gamsberg , Molecular evolution , Geology -- South Africa -- Namaqualand
- Description: The base metal massive sulfide deposits of the Aggeneys-Gamsberg (A-G) District are hosted within the Mesoproterozoic Bushmanland Group of the Namaqua-Natal Metamorphic Complex in the Northern Cape Province of South Africa. The district displays an apparent eastward trend in the economic concentration of base metals (+ barite) from relatively Cu-Pb-rich, Ba-poor mineralisation at Black Mountain to Zn- and Ba-rich ores at Gamsberg. Base metal sulfides at Gamsberg are restricted to the so called Gams (Iron) Formation which comprises a sulfidic mineralized unit (“B”) enveloped within a sequence of meta-sedimentary units (“A” and “C”). The aim of the study was to shed further light on the genesis and chemical evolution of the sulfide mineralisation at Gamsberg in the context of the entire A-G District, by interrogating further the apparent district-wide trend in base metal distribution. The Gams Iron Formation was sampled and studied from one key drill core intersection (“G1”) which intersects the largest part of it as described elsewhere; a small number of additional samples from a second drill core (“G2”) complemented the main sample suite. Minerals that make up the silicate assemblages across the studied section include quartz, garnet, pyroxene, pyroxenoid, phyllosilicates, carbonates, amphiboles, oxides (chiefly magnetite) and graphite. In a stratigraphic context, the mineralogical variations conform directly to those documented in the relevant literature from the Gamsberg locality. These are coupled, where possible, with mineral-chemical profiles of selected silicate species which replicate those of bulk-rock compositions, particularly with respect to Mn, Fe and Ca in the upper C Unit of the studied section. These signals collectively track the characteristic transition from a terrigenous, siliciclastic sediment-dominated footwall to an exhalative sediment-dominated hanging wall to the sulfide mineralisation as also seen in similar deposits elsewhere, particularly with respect to the characteristic Mn-rich signature increasingly observed in the hanging wall C Unit. The foregoing suggests that the examined section faithfully records the interpreted primary stratigraphy of the deposits, despite the complex structural and metamorphic overprint that characterises the region. This facilitates a stratigraphic analytical approach on the sulfidic Unit B, through a combination of mineral-chemical and stable isotope analyses. Dominant sulfides in Unit B are sphalerite and pyrite, with lesser pyrrhotite and minor galena. Sphalerite shows high and generally invariant contents of Fe (mean 12.18wt%, as FeS) whereas Zn anti-correlates with Mn (mean 5.58wt%, as MnS). Isotopic analyses for S, Fe and Zn in hand-picked sphalerite and pyrite separates were used with a view to providing new evidence for chemical and isotopic variation within the sulfide ore-body in a vertical (i.e. stratigraphic) sense, discuss the implications thereof, and ultimately interpret the new data in light of similar existing data from the A-G District and elsewhere. The δ³⁴S data for pyrite (plus a single pyrrhotite grain) and sphalerite from both cores G1 and G2 show comparable compositional ranges between 22.9 and 30.4‰ and between 27 and 30.1‰ respectively. The δ⁵⁶Fe data for pyrite show a range between -1.85 and 0.19‰, whereas seven sphalerite separates have a very narrow range of δ⁶⁶Zn from 0.06 to 0.20‰. The atypically high sulfur isotope data reported in this study are interpreted to reflect sedimentary deposition of primary sulfide ore at Gamsberg from an isotopically highly evolved seawater sulfate source through large-scale Rayleigh fractionation processes. Thermogenic sulfate reduction is proposed to have been the main reductive mechanism from seawater sulfate to sulfide, given the absence of very low δ³⁴S data for sulfides anywhere in the A-G District. By contrast, the δ⁶⁶Zn values for sphalerite are for all intents and purposes invariant and very close to 0‰, and therefore suggest little Zn isotope fractionation from an original exhalative fluid source. On this evidence alone, Zn isotopes therefore appear to hold little promise as a proxy of the chemical and isotopic evolution of SEDEX deposits in space and time, although this can only be verified through further application in the broader A-G District and similar deposits elsewhere. The apparent decoupling of Zn and S isotopes in the Gamsberg sulfide deposit, however, points towards diverse sources of these two components, i.e. ascending metalliferous brines versus seawater respectively. Finally, pyrite δ⁵⁶Fe data do show a stratigraphic trend of generally declining values up-section, which are interpreted to reflect the influence of broadly coeval precipitation of isotopically heavy Fe-oxides on a broader-scale – now preserved as abundant magnetite through metamorphism. Further work on the iron isotope composition of silicate-and oxide-hosted Fe on a local-to-district scale will assist in testing this interpretation.
- Full Text:
New possibilities for research on reef fish across the continental shelf of South Africa
- Bernard, Anthony T F, Gotz, A, Parker, Daniel M, Heyns, Elodie R, Halse, Sarah J, Riddin, N A, Smith, M K S, Paterson, Angus W, Winker, A Henning, Fullwood, L, Langlois, T J, Harvey, E S
- Authors: Bernard, Anthony T F , Gotz, A , Parker, Daniel M , Heyns, Elodie R , Halse, Sarah J , Riddin, N A , Smith, M K S , Paterson, Angus W , Winker, A Henning , Fullwood, L , Langlois, T J , Harvey, E S
- Date: 2014
- Language: English
- Type: Article
- Identifier: vital:6971 , http://hdl.handle.net/10962/d1014566
- Description: [From introduction] Subtidal research presents numerous challenges that restrict the ability to answer fundamental ecological questions related to reef systems. These challenges are closely associated with traditional monitoring methods and include depth restrictions (e.g. safe diving depths for underwater visual census), habitat destruction (e.g. trawling), mortality of target species (e.g. controlled angling and fish traps), and high operating costs (e.g. remotely operated vehicles and large research vessels. Whereas many of these challenges do not apply or are avoidable in the shallow subtidal environment, the difficulties grow as one attempts to sample deeper benthic habitats. This situation has resulted in a paucity of knowledge on the structure and ecology of deep water reef habitats around the coast of South Africa and in most marine areas around the world. Furthermore, the inability to effectively survey deep water benthic environments has limited the capacity of researchers to investigate connectivity between shallow and deep water habitats in a standardised and comparable fashion.
- Full Text:
- Authors: Bernard, Anthony T F , Gotz, A , Parker, Daniel M , Heyns, Elodie R , Halse, Sarah J , Riddin, N A , Smith, M K S , Paterson, Angus W , Winker, A Henning , Fullwood, L , Langlois, T J , Harvey, E S
- Date: 2014
- Language: English
- Type: Article
- Identifier: vital:6971 , http://hdl.handle.net/10962/d1014566
- Description: [From introduction] Subtidal research presents numerous challenges that restrict the ability to answer fundamental ecological questions related to reef systems. These challenges are closely associated with traditional monitoring methods and include depth restrictions (e.g. safe diving depths for underwater visual census), habitat destruction (e.g. trawling), mortality of target species (e.g. controlled angling and fish traps), and high operating costs (e.g. remotely operated vehicles and large research vessels. Whereas many of these challenges do not apply or are avoidable in the shallow subtidal environment, the difficulties grow as one attempts to sample deeper benthic habitats. This situation has resulted in a paucity of knowledge on the structure and ecology of deep water reef habitats around the coast of South Africa and in most marine areas around the world. Furthermore, the inability to effectively survey deep water benthic environments has limited the capacity of researchers to investigate connectivity between shallow and deep water habitats in a standardised and comparable fashion.
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Nonlinear optical studies of metallophtalocyanines and hemiporphyrazines in solution
- Authors: Britton, Jonathan
- Date: 2014
- Subjects: Phthalocyanines Photochemistry Nanoparticles Nanostructured materials Polymers Quantum dots
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4464 , http://hdl.handle.net/10962/d1011608
- Description: This thesis presents the study of the effects of CdTe-TGA quantum dots (QDs) on optical limiting ability of different phthalocyanine (Pc) complexes (5-12) containing Zn, Ga, In central metals and substituted with benzyloxyphenoxy, phenoxy, tertbutylphenoxy and amino groups in solution and in poly (methyl methacrylate) (PMMA) films. The optical limiting parameters of Pcs were higher for tertbutylphenoxy when compared to benzyloxyphenoxy and phenoxy substituents, in DMSO. Non-peripheral substitution decreased the optical limiting parameters. Third-order susceptibility (Im[χ⁽³⁾]/α) values of Pcs in the absence and presence of CdTe QDs were in the 10⁻¹² to 10⁻¹° esu cm range. Hyperpolarizabilities (γ) ranged from 10⁻³¹ to 10⁻²⁹ esu L for Pc alone or in mixture with QDs. The effect on the optical limiting abilities of twelve embedded phthalocyanines containing In, Ga, Zn and Al as central metals in polymer thin films was also examined. The effect of forming a covalent link zinc tetraamino phthalocyanine (12) with poly (methyl acrylic acid) (PMAA) and Zn (13) and OHAl (14) octacarboxy phthalocyanines to polyethylenimine (PEI) was also studied. The hyperpolarizability of the twelve phthalocyanines in polymer was found to be in the range of 10⁻²⁶ to 10⁻²⁴ esu.L. This is significantly higher than the hyperpolarizabilities of these phthalocyanines in solution. Non-linear optical (NLO) parameters were determined for phthalocyanine complexes containing In, Ga and Zn as central metals when embedded in PMMA polymer in the presence of quantum dots (QDs). The QDs mainly employed were CdTe-TGA (TGA = thioglylcolic acid). Triplet lifetimes increased as k (excited state (σex) to ground state (σg) absorption cross section ratio) values decreased with the addition of the CdTe-TGA to the phthalocyanines. The saturation energy density (Fsat) values were smaller in the films when compared to the solutions. Complex 7 tetrasubstituted with tert-butylphenoxy groups at non-peripheral positions was also studied in the presence of CdS-TGA, CdSe-TGA, fullerenes and single walled carbon nanotubes. There is a general improvement in optical limiting ability of Pc complexes in the presence of nanomaterials (NMs). Degradation studies seem to indicate that placing a phthalocyanine within a polymer thin film may protect it slightly from photo- and thermal degradation. 3(4), 15(16)-Bis-(4 -tert-butyl-phenoxy)-10, 22-diaminohemiporphyrazinato chloroindium hemiporphyrazine was synthesized from 1, 3, 5-triaminobenzene and 4-tert-butyl-phenoxyisoindoline. The structure of the complex was confirmed using mass, nuclear magnetic resonance and infrared spectroscopies. The nonlinear parameters of the compound was also analyzed in dimethylformamide and found to be significantly greater than previously analyzed phthalocyanines.
- Full Text:
- Authors: Britton, Jonathan
- Date: 2014
- Subjects: Phthalocyanines Photochemistry Nanoparticles Nanostructured materials Polymers Quantum dots
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4464 , http://hdl.handle.net/10962/d1011608
- Description: This thesis presents the study of the effects of CdTe-TGA quantum dots (QDs) on optical limiting ability of different phthalocyanine (Pc) complexes (5-12) containing Zn, Ga, In central metals and substituted with benzyloxyphenoxy, phenoxy, tertbutylphenoxy and amino groups in solution and in poly (methyl methacrylate) (PMMA) films. The optical limiting parameters of Pcs were higher for tertbutylphenoxy when compared to benzyloxyphenoxy and phenoxy substituents, in DMSO. Non-peripheral substitution decreased the optical limiting parameters. Third-order susceptibility (Im[χ⁽³⁾]/α) values of Pcs in the absence and presence of CdTe QDs were in the 10⁻¹² to 10⁻¹° esu cm range. Hyperpolarizabilities (γ) ranged from 10⁻³¹ to 10⁻²⁹ esu L for Pc alone or in mixture with QDs. The effect on the optical limiting abilities of twelve embedded phthalocyanines containing In, Ga, Zn and Al as central metals in polymer thin films was also examined. The effect of forming a covalent link zinc tetraamino phthalocyanine (12) with poly (methyl acrylic acid) (PMAA) and Zn (13) and OHAl (14) octacarboxy phthalocyanines to polyethylenimine (PEI) was also studied. The hyperpolarizability of the twelve phthalocyanines in polymer was found to be in the range of 10⁻²⁶ to 10⁻²⁴ esu.L. This is significantly higher than the hyperpolarizabilities of these phthalocyanines in solution. Non-linear optical (NLO) parameters were determined for phthalocyanine complexes containing In, Ga and Zn as central metals when embedded in PMMA polymer in the presence of quantum dots (QDs). The QDs mainly employed were CdTe-TGA (TGA = thioglylcolic acid). Triplet lifetimes increased as k (excited state (σex) to ground state (σg) absorption cross section ratio) values decreased with the addition of the CdTe-TGA to the phthalocyanines. The saturation energy density (Fsat) values were smaller in the films when compared to the solutions. Complex 7 tetrasubstituted with tert-butylphenoxy groups at non-peripheral positions was also studied in the presence of CdS-TGA, CdSe-TGA, fullerenes and single walled carbon nanotubes. There is a general improvement in optical limiting ability of Pc complexes in the presence of nanomaterials (NMs). Degradation studies seem to indicate that placing a phthalocyanine within a polymer thin film may protect it slightly from photo- and thermal degradation. 3(4), 15(16)-Bis-(4 -tert-butyl-phenoxy)-10, 22-diaminohemiporphyrazinato chloroindium hemiporphyrazine was synthesized from 1, 3, 5-triaminobenzene and 4-tert-butyl-phenoxyisoindoline. The structure of the complex was confirmed using mass, nuclear magnetic resonance and infrared spectroscopies. The nonlinear parameters of the compound was also analyzed in dimethylformamide and found to be significantly greater than previously analyzed phthalocyanines.
- Full Text:
Normative self-perceptions of journalists in Nigeria : the case of the Guardian newspaper
- Authors: Tiri, Judith
- Date: 2014
- Subjects: Guardian (Nigeria) , Nigeria -- In mass media , Nigeria -- Politics and government -- In mass media , Newspapers -- Nigeria , Journalism -- Political aspects -- Nigeria , Journalists -- Nigeria -- Psychology
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:3523
- Description: The study aims at interrogating the self - perceptions of journalists in Nigeria. The study is an attempt to answer some questions as: what contributions have journalists made to the democratization of Nigeria from 1960 to date? What role(s) did the media play during and after the transition to democracy? To what extent have the activities of politicians and the business class affected t he media’s social responsibility? What are the self-perceptions of journalists working in Nigeria’s The Guardian newspaper? The studies on normative theories of the press, Journalism Culture, and the perceived influences on journalism practice in a democra cy were adapted to answer the afore-listed questions. The works on how elite continuity and transitology models affect the perceptions of journalists in new democracies were also used to answer the questions posed. Since the field of research of the preced ing works is the West, the Nigerian experience points to issues that were not addressed in the prior studies because of the latter’s unique socio-political, historical, economic and ethno-religious structures . The data were collected and analyzed according to the QualitaQualitative paradigm, using in-depth semi-structured individual interviews with journalists working at The Guardian newspaper. The findings suggest that the journalists have made positive contributions to Nigeria’s democratization. The journalists that support this thesis claim that the self-perceptions of their role have changed from an adversarial position to a democratically-defined social responsibility role. This is because journalists ensure that government policies are implemented and the iss ues that affect the masses are reported. The findings show that in spite of the shift to democratization some challenges have remained, for example the journalists’ lives are not safe ; they collect bribes which are popularly called brown envelopes in Nigeria, write biased stories, and hold partisan relationships with the politicians and entrepreneurial elites and so on. The study acknowledges that democratization is in a continuum and that (the stakeholders or) civil society, journalists, the state and the entrepreneurial elites must contribute to deepen Nigeria’s democracy. The study suggests a self-perception theory that uses individual structures and institutions of a country to guide the stakeholders to play roles that will deepen democracy.
- Full Text:
- Authors: Tiri, Judith
- Date: 2014
- Subjects: Guardian (Nigeria) , Nigeria -- In mass media , Nigeria -- Politics and government -- In mass media , Newspapers -- Nigeria , Journalism -- Political aspects -- Nigeria , Journalists -- Nigeria -- Psychology
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:3523
- Description: The study aims at interrogating the self - perceptions of journalists in Nigeria. The study is an attempt to answer some questions as: what contributions have journalists made to the democratization of Nigeria from 1960 to date? What role(s) did the media play during and after the transition to democracy? To what extent have the activities of politicians and the business class affected t he media’s social responsibility? What are the self-perceptions of journalists working in Nigeria’s The Guardian newspaper? The studies on normative theories of the press, Journalism Culture, and the perceived influences on journalism practice in a democra cy were adapted to answer the afore-listed questions. The works on how elite continuity and transitology models affect the perceptions of journalists in new democracies were also used to answer the questions posed. Since the field of research of the preced ing works is the West, the Nigerian experience points to issues that were not addressed in the prior studies because of the latter’s unique socio-political, historical, economic and ethno-religious structures . The data were collected and analyzed according to the QualitaQualitative paradigm, using in-depth semi-structured individual interviews with journalists working at The Guardian newspaper. The findings suggest that the journalists have made positive contributions to Nigeria’s democratization. The journalists that support this thesis claim that the self-perceptions of their role have changed from an adversarial position to a democratically-defined social responsibility role. This is because journalists ensure that government policies are implemented and the iss ues that affect the masses are reported. The findings show that in spite of the shift to democratization some challenges have remained, for example the journalists’ lives are not safe ; they collect bribes which are popularly called brown envelopes in Nigeria, write biased stories, and hold partisan relationships with the politicians and entrepreneurial elites and so on. The study acknowledges that democratization is in a continuum and that (the stakeholders or) civil society, journalists, the state and the entrepreneurial elites must contribute to deepen Nigeria’s democracy. The study suggests a self-perception theory that uses individual structures and institutions of a country to guide the stakeholders to play roles that will deepen democracy.
- Full Text:
Occurrence of larval fishes in a rocky shore-associated nursery area in temperate South Africa, with emphasis on temperature-related growth in dominant Sparidae
- Strydom, Nadine A, Booth, Anthony J, McLachlan, A
- Authors: Strydom, Nadine A , Booth, Anthony J , McLachlan, A
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/125342 , vital:35774 , https://doi.10.2989/1814232X.2014.899269
- Description: Larval fishes were studied in Shark Bay on the warm, temperate south-east coast of South Africa. The bay is a small, shallow, subtidal area associated with a rocky shore. Sampling took place fortnightly for a period of one year (September 2004–August 2005) to assess composition, abundance and growth of fishes. The objectives of the study were to assess the extent of use of this habitat type by larvae throughout the year and to ascertain what temperature advantages this relatively warm habitat could have on growth of dominant species. A total of 10 fish families, represented by 16 taxa, was collected using a specially modified beach seine net (mesh aperture 500 μm). Shark Bay was utilised extensively by Diplodus capensis and Sarpa salpa and to a lesser extent by Clinus supercilious, Liza spp. and Mugil cephalus. Mean catch per unit effort (CPUE) of larvae was high (>500 larvae per net haul), peaking at ~7 500 larvae in a single haul that consisted mostly of postflexion-stage Sparidae. There was a weak, negative correlation (−0.24) between temperature and overall CPUE, which reflected either the seasonality or protracted nature of spawning by the species occurring in the bay. There was no significant difference in CPUE between the moon phases sampled on the spring tides in this study. Shark Bay was dominated by postflexionstage larvae, consisting in particular of species common to tide pools during the juvenile stage. Certain species were sampled for only short periods during the year. The year-round occurrence and high abundance of the two dominant species indicate that Shark Bay represents an important nursery habitat for the completion of the larval phase. These species exhibited exponential growth that lagged behind small increases in temperature, highlighting the importance of access to shallow, warm habitat that allows larval growth to increase, leading to earlier settlement into juvenile habitat and thereby reducing the pelagic larval duration.
- Full Text:
- Authors: Strydom, Nadine A , Booth, Anthony J , McLachlan, A
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/125342 , vital:35774 , https://doi.10.2989/1814232X.2014.899269
- Description: Larval fishes were studied in Shark Bay on the warm, temperate south-east coast of South Africa. The bay is a small, shallow, subtidal area associated with a rocky shore. Sampling took place fortnightly for a period of one year (September 2004–August 2005) to assess composition, abundance and growth of fishes. The objectives of the study were to assess the extent of use of this habitat type by larvae throughout the year and to ascertain what temperature advantages this relatively warm habitat could have on growth of dominant species. A total of 10 fish families, represented by 16 taxa, was collected using a specially modified beach seine net (mesh aperture 500 μm). Shark Bay was utilised extensively by Diplodus capensis and Sarpa salpa and to a lesser extent by Clinus supercilious, Liza spp. and Mugil cephalus. Mean catch per unit effort (CPUE) of larvae was high (>500 larvae per net haul), peaking at ~7 500 larvae in a single haul that consisted mostly of postflexion-stage Sparidae. There was a weak, negative correlation (−0.24) between temperature and overall CPUE, which reflected either the seasonality or protracted nature of spawning by the species occurring in the bay. There was no significant difference in CPUE between the moon phases sampled on the spring tides in this study. Shark Bay was dominated by postflexionstage larvae, consisting in particular of species common to tide pools during the juvenile stage. Certain species were sampled for only short periods during the year. The year-round occurrence and high abundance of the two dominant species indicate that Shark Bay represents an important nursery habitat for the completion of the larval phase. These species exhibited exponential growth that lagged behind small increases in temperature, highlighting the importance of access to shallow, warm habitat that allows larval growth to increase, leading to earlier settlement into juvenile habitat and thereby reducing the pelagic larval duration.
- Full Text:
Ocean warming affects the distribution and abundance of resident fishes by changing their reproductive scope
- Potts, Warren M, Booth, Anthony J, Richardson, Timothy J, Sauer, Warwick H H
- Authors: Potts, Warren M , Booth, Anthony J , Richardson, Timothy J , Sauer, Warwick H H
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/125352 , vital:35775 , https://doi.10.1007/s11160-013-9329-3
- Description: With ocean warming predicted globally, one of the mechanisms driving distributional shifts and changes in the abundance of resident fishes is reproductive output. The relationship between sea surface temperature and the reproductive activity of a eurythermic, resident coastal species, blacktail seabream Diplodus sargus capensis, was examined in the ‘‘ocean warming’’ hotspot of the northern Benguela. Reproductive activity was found to be restricted to periods when the water temperature dropped below 20 _C. A metadata analysis conducted on the D. sargus sub-species complex similarly showed that reproductive activity was restricted to temperatures between 15 and 20 _C, regardless of the range in ambient water temperature. Based on these findings and using satellite derived SST information, we examined D. s. capensis’s total and seasonal ‘‘reproductive scope’’ that is defined as either the area suitable for spawning each year or the duration of its potential spawning season at a fixed geographical locality, respectively. Trends were examined over the last three decades. Reproductive scope by area was found to be shrinking at a rate of 7 % per decade in southern Angola and expanding at a rate of 6 % per decade in northern Namibia. Reproductive scope by season decreased by 1.05 months per decade in Namibe, southern Angola and increased by 0.76 months per decade in Hentiesbaai, northern Namibia. Changes in reproductive scope may be a driving mechanism of distributional shifts in resident fishes, although the rate of the shifts is likely to be slow. More importantly, changes in reproductive scope will not be uniform throughout fish distributions and will most likely result in heterogeneous variations in fish abundance.
- Full Text:
- Authors: Potts, Warren M , Booth, Anthony J , Richardson, Timothy J , Sauer, Warwick H H
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/125352 , vital:35775 , https://doi.10.1007/s11160-013-9329-3
- Description: With ocean warming predicted globally, one of the mechanisms driving distributional shifts and changes in the abundance of resident fishes is reproductive output. The relationship between sea surface temperature and the reproductive activity of a eurythermic, resident coastal species, blacktail seabream Diplodus sargus capensis, was examined in the ‘‘ocean warming’’ hotspot of the northern Benguela. Reproductive activity was found to be restricted to periods when the water temperature dropped below 20 _C. A metadata analysis conducted on the D. sargus sub-species complex similarly showed that reproductive activity was restricted to temperatures between 15 and 20 _C, regardless of the range in ambient water temperature. Based on these findings and using satellite derived SST information, we examined D. s. capensis’s total and seasonal ‘‘reproductive scope’’ that is defined as either the area suitable for spawning each year or the duration of its potential spawning season at a fixed geographical locality, respectively. Trends were examined over the last three decades. Reproductive scope by area was found to be shrinking at a rate of 7 % per decade in southern Angola and expanding at a rate of 6 % per decade in northern Namibia. Reproductive scope by season decreased by 1.05 months per decade in Namibe, southern Angola and increased by 0.76 months per decade in Hentiesbaai, northern Namibia. Changes in reproductive scope may be a driving mechanism of distributional shifts in resident fishes, although the rate of the shifts is likely to be slow. More importantly, changes in reproductive scope will not be uniform throughout fish distributions and will most likely result in heterogeneous variations in fish abundance.
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Ocean warming hotspots provide early warning laboratories for climate change impacts
- Pecl, Gretta T, Hobday, Alistair J, Frusher, Stewart, Sauer, Warwick H H, Bates, Amanda E
- Authors: Pecl, Gretta T , Hobday, Alistair J , Frusher, Stewart , Sauer, Warwick H H , Bates, Amanda E
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/125363 , vital:35776 , https://doi.10.1007/s11160-014-9355-9
- Description: A growing literature describes a wide range of negative impacts of climate change on marine resources and the people and communities they support, including species range changes, changes in productivity of fisheries and declines in economic performance (Doney et al. 2012; Poloczanska et al. 2013). These impacts, many of which are projected to increase in future, are compounded by growing pressures on marine resources (Halpern et al. 2008; Maxwell et al. 2013). An estimated 260 million people are involved directly or indirectly in global marine fisheries (Teh and Sumaila 2013) with many of the resources for capture fisheries already fully (&57 % in 2009) or over exploited (30 %) (FAO 2012). Nevertheless, production of marine resources will need to increase to accommodate the demands of a growing population, and the impacts of climate change on food security will need to be minimised (FAO 2009). Identifying opportunities and threats, and developing adaptation options in response to climate change impacts in the marine realm, is essential for optimising the benefits that society can continue to derive from the goods and services provided by marine resources.
- Full Text:
- Authors: Pecl, Gretta T , Hobday, Alistair J , Frusher, Stewart , Sauer, Warwick H H , Bates, Amanda E
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/125363 , vital:35776 , https://doi.10.1007/s11160-014-9355-9
- Description: A growing literature describes a wide range of negative impacts of climate change on marine resources and the people and communities they support, including species range changes, changes in productivity of fisheries and declines in economic performance (Doney et al. 2012; Poloczanska et al. 2013). These impacts, many of which are projected to increase in future, are compounded by growing pressures on marine resources (Halpern et al. 2008; Maxwell et al. 2013). An estimated 260 million people are involved directly or indirectly in global marine fisheries (Teh and Sumaila 2013) with many of the resources for capture fisheries already fully (&57 % in 2009) or over exploited (30 %) (FAO 2012). Nevertheless, production of marine resources will need to increase to accommodate the demands of a growing population, and the impacts of climate change on food security will need to be minimised (FAO 2009). Identifying opportunities and threats, and developing adaptation options in response to climate change impacts in the marine realm, is essential for optimising the benefits that society can continue to derive from the goods and services provided by marine resources.
- Full Text:
Ocean warming, a rapid distributional shift, and the hybridization of a coastal fish species
- Potts, Warren M, Henriques, Romina, Santos, Carmen V D, Munnik, Kate, Ansorge, Isabelle J, Dufois, Francois, Sauer, Warwick H H, Booth, Anthony J, Kirchner, Carola, Sauer, Warwick, Shaw, Paul W
- Authors: Potts, Warren M , Henriques, Romina , Santos, Carmen V D , Munnik, Kate , Ansorge, Isabelle J , Dufois, Francois , Sauer, Warwick H H , Booth, Anthony J , Kirchner, Carola , Sauer, Warwick , Shaw, Paul W
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/125375 , vital:35777 , https://doi.10.1111/gcb.12612
- Description: Despite increasing awareness of large-scale climate-driven distribution shifts in the marine environment, no study has linked rapid ocean warming to a shift in distribution and consequent hybridization of a marine fish species. This study describes rapid warming (0.8 °C per decade) in the coastal waters of the Angola-Benguela Frontal Zone over the last three decades and a concomitant shift by a temperature sensitive coastal fish species (Argyrosomus coronus) southward from Angola into Namibia. In this context, rapid shifts in distribution across Economic Exclusive Zones will complicate the management of fishes, particularly when there is a lack of congruence in the fisheries policy between nations. Evidence for recent hybridization between A. coronus and a congener, A. inodorus, indicate that the rapid shift in distribution of A. coronus has placed adults of the two species in contact during their spawning events. Ocean warming may therefore revert established species isolation mechanisms and alter the evolutionary history of fishes. While the consequences of the hybridization on the production of the resource remain unclear, this will most likely introduce additional layers of complexity to their management.
- Full Text:
- Authors: Potts, Warren M , Henriques, Romina , Santos, Carmen V D , Munnik, Kate , Ansorge, Isabelle J , Dufois, Francois , Sauer, Warwick H H , Booth, Anthony J , Kirchner, Carola , Sauer, Warwick , Shaw, Paul W
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/125375 , vital:35777 , https://doi.10.1111/gcb.12612
- Description: Despite increasing awareness of large-scale climate-driven distribution shifts in the marine environment, no study has linked rapid ocean warming to a shift in distribution and consequent hybridization of a marine fish species. This study describes rapid warming (0.8 °C per decade) in the coastal waters of the Angola-Benguela Frontal Zone over the last three decades and a concomitant shift by a temperature sensitive coastal fish species (Argyrosomus coronus) southward from Angola into Namibia. In this context, rapid shifts in distribution across Economic Exclusive Zones will complicate the management of fishes, particularly when there is a lack of congruence in the fisheries policy between nations. Evidence for recent hybridization between A. coronus and a congener, A. inodorus, indicate that the rapid shift in distribution of A. coronus has placed adults of the two species in contact during their spawning events. Ocean warming may therefore revert established species isolation mechanisms and alter the evolutionary history of fishes. While the consequences of the hybridization on the production of the resource remain unclear, this will most likely introduce additional layers of complexity to their management.
- Full Text:
On the viability of pro-active automated PII breach detection: A South African case study
- Swart, Ignus, Irwin, Barry V W, Grobler, Marthie
- Authors: Swart, Ignus , Irwin, Barry V W , Grobler, Marthie
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/430235 , vital:72676 , https://doi.org/10.1145/2664591.2664600
- Description: Various reasons exist why certain types of information is deemed personal both by legislation and society. While crimes such as identity theft and impersonation have always been in existence, the rise of the internet and social media has exacerbated the problem. South Africa has recently joined the growing ranks of countries passing legislation to ensure the privacy of certain types of data. As is the case with most implemented security enforcement systems, most appointed privacy regulators operate in a reactive way. While this is a completely acceptable method of operation, it is not the most efficient. Research has shown that most data leaks containing personal information remains available for more than a month on average before being detected and reported. Quite often the data is discovered by a third party who selects to notify the responsible organisation but can just as easily copy the data and make use of it. This paper will display the potential benefit a privacy regulator can expect to see by implementing pro-active detection of electronic personally identifiable information (PII). Adopting pro-active detection of PII exposed on public networks can potentially contribute to a significant reduction in exposure time. The results discussed in this paper were obtained by means of experimentation on a custom created PII detection system.
- Full Text:
- Authors: Swart, Ignus , Irwin, Barry V W , Grobler, Marthie
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/430235 , vital:72676 , https://doi.org/10.1145/2664591.2664600
- Description: Various reasons exist why certain types of information is deemed personal both by legislation and society. While crimes such as identity theft and impersonation have always been in existence, the rise of the internet and social media has exacerbated the problem. South Africa has recently joined the growing ranks of countries passing legislation to ensure the privacy of certain types of data. As is the case with most implemented security enforcement systems, most appointed privacy regulators operate in a reactive way. While this is a completely acceptable method of operation, it is not the most efficient. Research has shown that most data leaks containing personal information remains available for more than a month on average before being detected and reported. Quite often the data is discovered by a third party who selects to notify the responsible organisation but can just as easily copy the data and make use of it. This paper will display the potential benefit a privacy regulator can expect to see by implementing pro-active detection of electronic personally identifiable information (PII). Adopting pro-active detection of PII exposed on public networks can potentially contribute to a significant reduction in exposure time. The results discussed in this paper were obtained by means of experimentation on a custom created PII detection system.
- Full Text:
One leg at a time
- Authors: Vivier, Lincky Elmé
- Date: 2014
- Subjects: Creative writing (Higher education) -- Research -- South Africa , Creative writing -- Poetry , South African poetry (English) -- Study and teaching (Higher) , South African poetry (English) -- 21st century , English language -- Writing
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:5974 , http://hdl.handle.net/10962/d1012945
- Description: This collection of poems explores the boundaries between certainty and uncertainty, between the desire for meaning and the destabilisation of meaning. The content encompasses everyday life, love and loss, and the ambiguities are reflected in the forms used, so that, for instance, the linear continuity of narrative and the musicality of the lyric may be juxtaposed with the fragmented and imagistic leaps of the associative poem.
- Full Text:
- Authors: Vivier, Lincky Elmé
- Date: 2014
- Subjects: Creative writing (Higher education) -- Research -- South Africa , Creative writing -- Poetry , South African poetry (English) -- Study and teaching (Higher) , South African poetry (English) -- 21st century , English language -- Writing
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:5974 , http://hdl.handle.net/10962/d1012945
- Description: This collection of poems explores the boundaries between certainty and uncertainty, between the desire for meaning and the destabilisation of meaning. The content encompasses everyday life, love and loss, and the ambiguities are reflected in the forms used, so that, for instance, the linear continuity of narrative and the musicality of the lyric may be juxtaposed with the fragmented and imagistic leaps of the associative poem.
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Ontogenetic and seasonal shifts in the diet of Diplodus cervinus hottentotus (Pisces: Sparidae) in southern Angola
- Winkler, Alexander C, Santos, Carmen V D, Potts, Warren M
- Authors: Winkler, Alexander C , Santos, Carmen V D , Potts, Warren M
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/125452 , vital:35784 , https://doi.10.2989/1814232X.2014.951392
- Description: Fishes of the family Sparidae occupy a diverse range of trophic niches, from herbivores to generalist omnivores and specialist predators (Hanel and Tsigenopoulos 2011). Feeding specialisation in this family is facilitated by diversity in tooth type and anterior jaw arrangement (Vandewalle et al. 1995). Other fish families, such as Cyprinidae and Labridae, have developed crushing pharyngeal teeth to process their food. Sparids, however, have retained a simple pharyngeal tooth arrangement and instead have developed molariform teeth to process hard-shelled molluscs and invertebrate prey. Hanel and Tsigenopoulos (2011) suggested that this alternate strategy is a major factor facilitating the trophic diversity in sparid fishes.
- Full Text:
- Authors: Winkler, Alexander C , Santos, Carmen V D , Potts, Warren M
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/125452 , vital:35784 , https://doi.10.2989/1814232X.2014.951392
- Description: Fishes of the family Sparidae occupy a diverse range of trophic niches, from herbivores to generalist omnivores and specialist predators (Hanel and Tsigenopoulos 2011). Feeding specialisation in this family is facilitated by diversity in tooth type and anterior jaw arrangement (Vandewalle et al. 1995). Other fish families, such as Cyprinidae and Labridae, have developed crushing pharyngeal teeth to process their food. Sparids, however, have retained a simple pharyngeal tooth arrangement and instead have developed molariform teeth to process hard-shelled molluscs and invertebrate prey. Hanel and Tsigenopoulos (2011) suggested that this alternate strategy is a major factor facilitating the trophic diversity in sparid fishes.
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Optical nonlinearities and photophysicochemical behaviour of green and blue forms of lutetium bisphthalocyanines
- Sekhosana, Kutloano Edward, Amuhaya, Edith, Mack, John, Nyokong, Tebello
- Authors: Sekhosana, Kutloano Edward , Amuhaya, Edith , Mack, John , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241606 , vital:50954 , xlink:href="https://doi.org/10.1039/C4TC00505H"
- Description: A rare earth sandwich-type phthalocyanine: bis-{2,3,9,10,16,17,23,24-octa(4-tert-butylphenoxy) phthalocyaninato} lutetium(III) has been synthesized. The photophysical and nonlinear optical behavior of both the “green” and “blue” forms ([LuIIIPc2] and [LuIIIPc2]−, respectively) of the complex have been investigated. High triplet state and singlet oxygen quantum yield values were obtained for the neutral blue form which contains no unpaired electrons. Relatively high third order susceptibility and hyperpolarizability values of the order of 10−10 and 10−28 esu were obtained for both the green and blue forms, respectively. A very low threshold intensity of 0.00051 J cm−2 was obtained for the blue form. Hence the complex shows promise for non-linear optical applications.
- Full Text:
- Authors: Sekhosana, Kutloano Edward , Amuhaya, Edith , Mack, John , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241606 , vital:50954 , xlink:href="https://doi.org/10.1039/C4TC00505H"
- Description: A rare earth sandwich-type phthalocyanine: bis-{2,3,9,10,16,17,23,24-octa(4-tert-butylphenoxy) phthalocyaninato} lutetium(III) has been synthesized. The photophysical and nonlinear optical behavior of both the “green” and “blue” forms ([LuIIIPc2] and [LuIIIPc2]−, respectively) of the complex have been investigated. High triplet state and singlet oxygen quantum yield values were obtained for the neutral blue form which contains no unpaired electrons. Relatively high third order susceptibility and hyperpolarizability values of the order of 10−10 and 10−28 esu were obtained for both the green and blue forms, respectively. A very low threshold intensity of 0.00051 J cm−2 was obtained for the blue form. Hence the complex shows promise for non-linear optical applications.
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Optical nonlinearities in non-peripherally substituted pyridyloxy phthalocyanines
- Sanusi, Kayode, Antunes, Edith M, Nyokong, Tebello
- Authors: Sanusi, Kayode , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241618 , vital:50955 , xlink:href="https://doi.org/10.1039/C3DT52462K"
- Description: The optical nonlinearities of six non-peripherally-substituted pyridyloxy phthalocyanines have been studied at 532 nm using a nanosecond Z-scan technique in a dimethyl sulphoxide solution. Ring-strain effects and the absence of a metal center were found to greatly reduce the inherent high nonlinearities expected of some of these phthalocyanine complexes. Of the six molecules investigated, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyaninato lead(II) 3, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyanine 5, and 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyanine 6 were found to exhibit negligible nonlinear optical behavior, due to either the absence of asymmetry or central metal and/or the presence of a ring-strain effect. A two-photon absorption process was found to be the major contributor to the observed reverse saturable absorption (RSA) in 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyaninato lead(II) 4, 1(4)-mono-(2-pyridyloxy)phthalocyaninato lead(II) 7, and 1(4)-mono-(4-pyridyloxy)phthalocyaninato lead(II) 8, with large two-photon absorption cross-section, high hyperpolarizability and high third-order susceptibility values in the range of 4.53 × 10−43–5.33 × 10−42 cm4 s per photon, 1.61 × 10−28–1.89 × 10−27 esu and 9.73 × 10−12–7.05 × 10−11 esu respectively.
- Full Text:
- Authors: Sanusi, Kayode , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241618 , vital:50955 , xlink:href="https://doi.org/10.1039/C3DT52462K"
- Description: The optical nonlinearities of six non-peripherally-substituted pyridyloxy phthalocyanines have been studied at 532 nm using a nanosecond Z-scan technique in a dimethyl sulphoxide solution. Ring-strain effects and the absence of a metal center were found to greatly reduce the inherent high nonlinearities expected of some of these phthalocyanine complexes. Of the six molecules investigated, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyaninato lead(II) 3, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyanine 5, and 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyanine 6 were found to exhibit negligible nonlinear optical behavior, due to either the absence of asymmetry or central metal and/or the presence of a ring-strain effect. A two-photon absorption process was found to be the major contributor to the observed reverse saturable absorption (RSA) in 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyaninato lead(II) 4, 1(4)-mono-(2-pyridyloxy)phthalocyaninato lead(II) 7, and 1(4)-mono-(4-pyridyloxy)phthalocyaninato lead(II) 8, with large two-photon absorption cross-section, high hyperpolarizability and high third-order susceptibility values in the range of 4.53 × 10−43–5.33 × 10−42 cm4 s per photon, 1.61 × 10−28–1.89 × 10−27 esu and 9.73 × 10−12–7.05 × 10−11 esu respectively.
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Optimizing MIDAS III over South Africa
- Authors: Giday, Nigussie Mezgebe
- Date: 2014
- Subjects: Multi-Instrument Data Analysis System (MIDAS) , Global Positioning System , Ionosphere -- South Africa , Ionospheric electron density -- South Africa , Ionosondes -- South Africa , Tomography -- Scientific applications -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5517 , http://hdl.handle.net/10962/d1011277 , Multi-Instrument Data Analysis System (MIDAS) , Global Positioning System , Ionosphere -- South Africa , Ionospheric electron density -- South Africa , Ionosondes -- South Africa , Tomography -- Scientific applications -- South Africa
- Description: In this thesis an ionospheric tomographic algorithm called Multi-Instrument Data Anal- ysis System (MIDAS) is used to reconstruct electron density profiles using the Global Positioning System (GPS) data recorded from 53 GPS receivers over the South African region. MIDAS, developed by the Invert group at the University of Bath in the UK, is an inversion algorithm that produces a time dependent 3D image of the electron density of the ionosphere. GPS receivers record the time delay and phase advance of the trans- ionospheric GPS signals that traverse through the ionosphere from which the ionospheric parameter called Total Electron Content (TEC) can be computed. TEC, the line integral of the electron density along the satellite-receiver signal path, is ingested by ionospheric tomographic algorithms such as MIDAS to produce a time dependent 3D electron density profile. In order to validate electron density profiles from MIDAS, MIDAS derived NmF2 values were compared with ionosonde derived NmF2 values extracted from their respective 1D electron density profiles at 15 minute intervals for all four South African ionosonde stations (Grahamstown, Hermanus, Louisvale, and Madimbo). MIDAS 2D images of the electron density showed good diurnal and seasonal patterns; where a comparison of the 2D images at 12h00 UT for all the validation days exhibited maximum electron concentration during the autumn and summer and a minimum during the winter. A root mean square error (rmse) value as small as 0.88x 10¹¹[el=m³] was calculated for the Louisvale ionosonde station during the winter season and a maximum rmse value of 1.92x 10¹¹[el=m³] was ob- tained during the autumn season. The r² values were the least during the autumn and relatively large during summer and winter; similarly the rmse values were found to be a maximum during the autumn and a minimum during the winter indicating that MIDAS performs better during the winter than during the autumn and spring seasons. It is also observed that MIDAS performs better at Louisvale and Madimbo than at Grahamstown and Hermanus. In conclusion, the MIDAS reconstruction has showed good agreement with the ionosonde measurements; therefore, MIDAS can be considered a useful tool to study the ionosphere over the South African region.
- Full Text:
- Authors: Giday, Nigussie Mezgebe
- Date: 2014
- Subjects: Multi-Instrument Data Analysis System (MIDAS) , Global Positioning System , Ionosphere -- South Africa , Ionospheric electron density -- South Africa , Ionosondes -- South Africa , Tomography -- Scientific applications -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5517 , http://hdl.handle.net/10962/d1011277 , Multi-Instrument Data Analysis System (MIDAS) , Global Positioning System , Ionosphere -- South Africa , Ionospheric electron density -- South Africa , Ionosondes -- South Africa , Tomography -- Scientific applications -- South Africa
- Description: In this thesis an ionospheric tomographic algorithm called Multi-Instrument Data Anal- ysis System (MIDAS) is used to reconstruct electron density profiles using the Global Positioning System (GPS) data recorded from 53 GPS receivers over the South African region. MIDAS, developed by the Invert group at the University of Bath in the UK, is an inversion algorithm that produces a time dependent 3D image of the electron density of the ionosphere. GPS receivers record the time delay and phase advance of the trans- ionospheric GPS signals that traverse through the ionosphere from which the ionospheric parameter called Total Electron Content (TEC) can be computed. TEC, the line integral of the electron density along the satellite-receiver signal path, is ingested by ionospheric tomographic algorithms such as MIDAS to produce a time dependent 3D electron density profile. In order to validate electron density profiles from MIDAS, MIDAS derived NmF2 values were compared with ionosonde derived NmF2 values extracted from their respective 1D electron density profiles at 15 minute intervals for all four South African ionosonde stations (Grahamstown, Hermanus, Louisvale, and Madimbo). MIDAS 2D images of the electron density showed good diurnal and seasonal patterns; where a comparison of the 2D images at 12h00 UT for all the validation days exhibited maximum electron concentration during the autumn and summer and a minimum during the winter. A root mean square error (rmse) value as small as 0.88x 10¹¹[el=m³] was calculated for the Louisvale ionosonde station during the winter season and a maximum rmse value of 1.92x 10¹¹[el=m³] was ob- tained during the autumn season. The r² values were the least during the autumn and relatively large during summer and winter; similarly the rmse values were found to be a maximum during the autumn and a minimum during the winter indicating that MIDAS performs better during the winter than during the autumn and spring seasons. It is also observed that MIDAS performs better at Louisvale and Madimbo than at Grahamstown and Hermanus. In conclusion, the MIDAS reconstruction has showed good agreement with the ionosonde measurements; therefore, MIDAS can be considered a useful tool to study the ionosphere over the South African region.
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Ordinary people and the media: the demotic turn
- Authors: Garman, Anthea
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/159880 , vital:40352 , DOI: 10.1080/02560054.2014.886661
- Description: In this latest book, Graeme Turner, who we have come to know as a thoughtful, perceptive and questioning cultural studies theorist, investigates what the crucial underlying shift is in the relation between the media and the people. This shift is evidenced by the increasing visibility of ordinary people (and their experiences and opinions) in what we consume. At the outset he sums up what he sees as a structural move from media as ‘mediator or perhaps a broadcaster of cultural identities’ to ‘translator or even an author of identities’ (p. 3).
- Full Text:
- Authors: Garman, Anthea
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/159880 , vital:40352 , DOI: 10.1080/02560054.2014.886661
- Description: In this latest book, Graeme Turner, who we have come to know as a thoughtful, perceptive and questioning cultural studies theorist, investigates what the crucial underlying shift is in the relation between the media and the people. This shift is evidenced by the increasing visibility of ordinary people (and their experiences and opinions) in what we consume. At the outset he sums up what he sees as a structural move from media as ‘mediator or perhaps a broadcaster of cultural identities’ to ‘translator or even an author of identities’ (p. 3).
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Ore distribution controls of the Navachab Gold Mine, Damara Belt, Karibib District, Namibia
- Authors: Slabbert, W L
- Date: 2014
- Subjects: Gold ores -- Namibia , Ore deposits -- Namibia
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5082 , http://hdl.handle.net/10962/d1016364
- Description: The Navachab Gold mine, an orogenic lode gold deposit, is located in the Karibib region of the Pan-African (ca. 550-500) Damara belt of central Namibia. Gold mineralisation is developed within the steeply NW dipping limb of the Karibib dome. Here, ore envelopes trend along three main orientations: a) trends shallowly towards the NE (the down plunge extent), b) trends sub-vertically in and along the down plunge extent and c) trends sub-horizontally across the down plunge extent. The down plunge extent represents the bulk of the gold mineralisation, hosting the only high grade ores mined at Navachab. As such, past work primarily focused on establishing the controls to the mineralisation observed here. The sub-vertical and sub–horizontal ore trends are seen as secondary, lower grade, being hosted in the footwall. By cutting pushbacks into the footwall, in an effort to regain access to high grade pit bottom, future gold production almost exclusively relies upon optimally mining these ores. This underlines the importance to investigate and outline the mineralising controls to the secondary ore trends. This study identified the following prevailing quartz vein sets developed within the footwall, set (1) dips shallowly towards the NE (conjugate vein set), (2) steeply towards the NW (bedding parallel veins) and (3) steeply towards the SE (S2 foliation parallel). The NW and SE dipping sets contain high average gold grades, occurring at an infrequent vein density. The NE dipping veins, as a result of occurrence density alone, was highlighted as the dominant gold hosting set. Veining occurred during the late stages of the NW-SE directed, sub-horizontal shortening (D2) event and is associated with top-to-the-NW thrusting and NW-verging folds. Re-Os molybdenite dating from auriferous quartz veins indicates mineralisation occurred at 525-520 Ma. As crustal shortening amplified the Karibib dome, flexural flow developed fractures along bedding planes, providing the control to bedding parallel veins (NW dipping). With continued crustal compression the dome later experienced fold lock up associated with reduced mean rock stress and sub-horizontal extension occurred along the steeply NW dipping limb. Horizontal extensional gashes sucked in fluids to form the shallowly NE dipping conjugate vein set. These features suggest the regional D2 strain as the first-order control to quartz vein development, down plunge and within the footwall ores. To further define the secondary ores, lithological and structural controls were evaluated on a more detailed local scale. With equal amounts of biotite schist and calc-silicate host rock (bulk of the footwall lithology) material analysed, the biotite schist units were found to contain a larger volume amount of quartz veins. The mineralisation incurred is also developed at higher average gold grades compared to that of the calc-silicates, demonstrating biotite schist having the optimal rheology for quartz vein emplacement. Normal faulting and thrusting occurs widespread, at all scale levels, across the footwall. These were primarily observed along bedding foliations and secondly at higher angles cutting across foliation. The study did not constrain the extent of these, but can conclude faulting plays a very prominent role in re-distributing the secondary ores parallel to bedding along sub-vertical trend planes. Great care should be placed in properly modelling these with 3D software such as Leapfrog. The Navachab gold mineralisation came about as a result of convergent and collisional tectonics activating metamorphic dehydration of the crustal metapelites. As these fluids ascended they absorbed gold from the crust, emplaced by either a magmatic or paleo-placer source. The gold enriched hydrothermal fluids amalgamated in large scale 1ste order structures (shearing of the steep NW limb of the Karibib Dome, the Mon Repos Thrust Zone) that acted as primary active fluid path ways. In the case of Navachab the gold enriched fluid fluxed along these pathways while interacting with fluid sinks related to a physical throttle (brittle schist, folding, bedding parallel shears) and/or a chemical trap (marbles). By summarising and detailing the fluid sinks and active fluid pathways identified by this and previous works, it is strongly recommended that a mineral approach system be designed and implemented as targeting model to lead future exploration endeavours.
- Full Text:
- Authors: Slabbert, W L
- Date: 2014
- Subjects: Gold ores -- Namibia , Ore deposits -- Namibia
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5082 , http://hdl.handle.net/10962/d1016364
- Description: The Navachab Gold mine, an orogenic lode gold deposit, is located in the Karibib region of the Pan-African (ca. 550-500) Damara belt of central Namibia. Gold mineralisation is developed within the steeply NW dipping limb of the Karibib dome. Here, ore envelopes trend along three main orientations: a) trends shallowly towards the NE (the down plunge extent), b) trends sub-vertically in and along the down plunge extent and c) trends sub-horizontally across the down plunge extent. The down plunge extent represents the bulk of the gold mineralisation, hosting the only high grade ores mined at Navachab. As such, past work primarily focused on establishing the controls to the mineralisation observed here. The sub-vertical and sub–horizontal ore trends are seen as secondary, lower grade, being hosted in the footwall. By cutting pushbacks into the footwall, in an effort to regain access to high grade pit bottom, future gold production almost exclusively relies upon optimally mining these ores. This underlines the importance to investigate and outline the mineralising controls to the secondary ore trends. This study identified the following prevailing quartz vein sets developed within the footwall, set (1) dips shallowly towards the NE (conjugate vein set), (2) steeply towards the NW (bedding parallel veins) and (3) steeply towards the SE (S2 foliation parallel). The NW and SE dipping sets contain high average gold grades, occurring at an infrequent vein density. The NE dipping veins, as a result of occurrence density alone, was highlighted as the dominant gold hosting set. Veining occurred during the late stages of the NW-SE directed, sub-horizontal shortening (D2) event and is associated with top-to-the-NW thrusting and NW-verging folds. Re-Os molybdenite dating from auriferous quartz veins indicates mineralisation occurred at 525-520 Ma. As crustal shortening amplified the Karibib dome, flexural flow developed fractures along bedding planes, providing the control to bedding parallel veins (NW dipping). With continued crustal compression the dome later experienced fold lock up associated with reduced mean rock stress and sub-horizontal extension occurred along the steeply NW dipping limb. Horizontal extensional gashes sucked in fluids to form the shallowly NE dipping conjugate vein set. These features suggest the regional D2 strain as the first-order control to quartz vein development, down plunge and within the footwall ores. To further define the secondary ores, lithological and structural controls were evaluated on a more detailed local scale. With equal amounts of biotite schist and calc-silicate host rock (bulk of the footwall lithology) material analysed, the biotite schist units were found to contain a larger volume amount of quartz veins. The mineralisation incurred is also developed at higher average gold grades compared to that of the calc-silicates, demonstrating biotite schist having the optimal rheology for quartz vein emplacement. Normal faulting and thrusting occurs widespread, at all scale levels, across the footwall. These were primarily observed along bedding foliations and secondly at higher angles cutting across foliation. The study did not constrain the extent of these, but can conclude faulting plays a very prominent role in re-distributing the secondary ores parallel to bedding along sub-vertical trend planes. Great care should be placed in properly modelling these with 3D software such as Leapfrog. The Navachab gold mineralisation came about as a result of convergent and collisional tectonics activating metamorphic dehydration of the crustal metapelites. As these fluids ascended they absorbed gold from the crust, emplaced by either a magmatic or paleo-placer source. The gold enriched hydrothermal fluids amalgamated in large scale 1ste order structures (shearing of the steep NW limb of the Karibib Dome, the Mon Repos Thrust Zone) that acted as primary active fluid path ways. In the case of Navachab the gold enriched fluid fluxed along these pathways while interacting with fluid sinks related to a physical throttle (brittle schist, folding, bedding parallel shears) and/or a chemical trap (marbles). By summarising and detailing the fluid sinks and active fluid pathways identified by this and previous works, it is strongly recommended that a mineral approach system be designed and implemented as targeting model to lead future exploration endeavours.
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Organisational culture and leadership competencies in ABSA Business Bank: Enterprise Business, Gauteng
- Authors: Funani, Simphiwe Vincent
- Date: 2014
- Subjects: ABSA Bank Corporate culture Organizational behavior Leadership Leadership -- Ability testing Business enterprises -- Personnel management Executives -- Training of Organizational effectiveness
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:824 , http://hdl.handle.net/10962/d1011286
- Description: From Integrative summary: This document consists of three sections namely, an evaluation report (section 1), literature review (section 2), and research methodology (section 3). The evaluation report sets out the terms of reference for the research as well as identifying the objectives of the research. It also contains a summary of the literature review section, as well as a research methodology section summary. The literature review section contains a detailed review of the literature used in this study. This section sets out by reviewing existing literature on the topic of leadership, discussing the key elements of organisational culture and includes a short discussion on the typologies of culture. The Competing Values Framework as an organisational culture typology is discussed in greater detail, since it forms the foundation upon which the measurement and data collection tools for this research are founded. The research methodology section explains the research methodology and design employed in this study. This section also addresses some of the ethical considerations for this research, as well as how the researcher addressed them. There is also a brief discussion on the limitations of the research and the application of the results. This research focused on a business unit within Absa Business Bank, named Enterprise Business Gauteng Region, with the aim of investigating the “current organisational culture” in the business unit and the leadership competencies profile of its 11 Sales Managers. This was to provide the basis and departure point for the strategic organisational culture change that the new business unit head would have wanted to effect as the business has a history of non-performance, which the new business unit head aims to change. In order to diagnose the “current organisational culture” type, an organisational culture measurement tool based on the Competing Values Framework was used. The Competing Values Framework is a four-category organisational culture typology developed by Cameron and Quinn. The framework is based on two dimensions, how stable or flexible the organisation is, and how externally or internally focused it is. This framework was also employed to establish the leadership competencies profile of Sales Managers, as observed and experienced by the frontline staff, as well as the “desired organisational culture”, as intended by the new business unit head. Through hypotheses testing, the research revealed a statistically significant difference in perceptions of culture between males and females in the business unit. The perceptions of the female frontline staff about the “current” business unit culture indicated that they find it not to be empowering and less allowing for individuality and risk taking when compared to the male staff. The research also concluded that there is no statistically significant difference between leadership competencies associated with the four categories of the Competing Values Framework in the business unit. Comparisons between the “current” and the “desired” organisational culture revealed a misalignment. The main recommendations to the new business unit head were to get the leadership competencies of the Sales Managers aligned with the “desired organisational culture” state, and drive a purposive organisational culture change effort. To support this culture change, the espoused values of the business unit would need to be aligned to the desired culture state. To address the differences in perceptions of culture between males and females the business unit head would need to be mindful of the greater need to empower women either in their current roles, or by way of promotions to senior roles.
- Full Text:
- Authors: Funani, Simphiwe Vincent
- Date: 2014
- Subjects: ABSA Bank Corporate culture Organizational behavior Leadership Leadership -- Ability testing Business enterprises -- Personnel management Executives -- Training of Organizational effectiveness
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:824 , http://hdl.handle.net/10962/d1011286
- Description: From Integrative summary: This document consists of three sections namely, an evaluation report (section 1), literature review (section 2), and research methodology (section 3). The evaluation report sets out the terms of reference for the research as well as identifying the objectives of the research. It also contains a summary of the literature review section, as well as a research methodology section summary. The literature review section contains a detailed review of the literature used in this study. This section sets out by reviewing existing literature on the topic of leadership, discussing the key elements of organisational culture and includes a short discussion on the typologies of culture. The Competing Values Framework as an organisational culture typology is discussed in greater detail, since it forms the foundation upon which the measurement and data collection tools for this research are founded. The research methodology section explains the research methodology and design employed in this study. This section also addresses some of the ethical considerations for this research, as well as how the researcher addressed them. There is also a brief discussion on the limitations of the research and the application of the results. This research focused on a business unit within Absa Business Bank, named Enterprise Business Gauteng Region, with the aim of investigating the “current organisational culture” in the business unit and the leadership competencies profile of its 11 Sales Managers. This was to provide the basis and departure point for the strategic organisational culture change that the new business unit head would have wanted to effect as the business has a history of non-performance, which the new business unit head aims to change. In order to diagnose the “current organisational culture” type, an organisational culture measurement tool based on the Competing Values Framework was used. The Competing Values Framework is a four-category organisational culture typology developed by Cameron and Quinn. The framework is based on two dimensions, how stable or flexible the organisation is, and how externally or internally focused it is. This framework was also employed to establish the leadership competencies profile of Sales Managers, as observed and experienced by the frontline staff, as well as the “desired organisational culture”, as intended by the new business unit head. Through hypotheses testing, the research revealed a statistically significant difference in perceptions of culture between males and females in the business unit. The perceptions of the female frontline staff about the “current” business unit culture indicated that they find it not to be empowering and less allowing for individuality and risk taking when compared to the male staff. The research also concluded that there is no statistically significant difference between leadership competencies associated with the four categories of the Competing Values Framework in the business unit. Comparisons between the “current” and the “desired” organisational culture revealed a misalignment. The main recommendations to the new business unit head were to get the leadership competencies of the Sales Managers aligned with the “desired organisational culture” state, and drive a purposive organisational culture change effort. To support this culture change, the espoused values of the business unit would need to be aligned to the desired culture state. To address the differences in perceptions of culture between males and females the business unit head would need to be mindful of the greater need to empower women either in their current roles, or by way of promotions to senior roles.
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Oxidative desulfurization of fuel oils-catalytic oxidation and adsorptive removal of organosulfur compounds
- Authors: Ogunlaja, Adeniyi Sunday
- Date: 2014
- Subjects: Organosulfur compounds , Organosulfur compounds -- Oxidation , Organosulfur compounds -- Absorption and adsorption , Petroleum as fuel , Catalysis , Imprinted polymers , Molecular imprinting , Nanofibers , Electrospinning
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4498 , http://hdl.handle.net/10962/d1013152
- Description: The syntheses and evaluation of oxidovanadium(IV) complexes as catalysts for the oxidation of refractory organosulfur compounds in fuels is presented. The sulfones produced from the oxidation reaction were removed from fuel oils by employing molecularly imprinted polymers (MIPs). The oxidovanadium(IV) homogeneous catalyst, [V ͥ ͮ O(sal-HBPD)], as well as its heterogeneous polymer supported derivatives, poly[V ͥ ͮ O(sal-AHBPD)] and poly[V ͥ ͮ O(allylSB-co-EGDMA)], were synthesized and fully characterized by elemental analysis, FTIR, UV-Vis, XPS, AFM, SEM, BET and single crystal XRD for [V ͥ ͮ O(sal-HBPD)]. The MIPs were also characterized by elemental analysis, FTIR, SEM, EDX and BET. The catalyzed oxidation of fuel oil model sulfur compounds, thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT), was conducted under batch and continuous flow processes at 40°C by using tert-butylhydroperoxide (t-BuOOH) as oxidant. The continuous flow oxidation process presented the highest overall conversions and very high selectivity for sulfones. Maximum oxidation conversions of 71%, 89%, 99% and 88% was achieved for TH, BT, DBT and 4,6-DMDBT respectively when poly[V ͥ ͮ O(allylSB-co-EGDMA)] was employed at a flow-rate of 1 mL/h with over 90% sulfone selectivity. The process was further applied to the oxidation of hydro-treated diesel containing 385 ± 4.6 ppm of sulfur (mainly dibenzothiophene and dibenzothiophene derivatives), and this resulted to a high sulfur oxidation yield (> 99%), thus producing polar sulfones which are extractible by polar solid phase extractants. Adsorption of the polar sulfone compounds was carried-out by employing MIPs which were fabricated through the formation of recognition sites complementary to oxidized sulfur-containing compounds (sulfones) on electrospun polybenzimidazole (PBI) nanofibers, cross-linked chitosan microspheres and electrospun chitosan nanofibers. Adsorption of benzothiophene sulfone (BTO₂), dibenzothiophene sulfone (DBTO₂) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO₂) on the various molecularly imprinted adsorbents presented a Freundlich (multi-layered) adsorption isotherm which indicated interaction of adsorbed organosulfur compounds. Maximum adsorption observed for BTO₂, DBTO₂ and 4,6-DMDBTO₂ respectively was 8.5 ± 0.6 mg/g, 7.0 ± 0.5 mg/g and 6.6 ± 0.7 mg/g when imprinted chitosan nanofibers were employed, 4.9 ± 0.5 mg/g, 4.2 ± 0.7 mg/g and 3.9 ± 0.6 mg/g on molecularly imprinted chitosan microspheres, and 28.5 ± 0.4 mg/g, 29.8 ± 2.2 mg/g and 20.1 ± 1.4 mg/g on molecularly imprinted PBI nanofibers. Application of electrospun chitosan nanofibers on oxidized hydro-treated diesel presented a sulfur removal capacity of 84%, leaving 62 ± 3.2 ppm S in the fuel, while imprinted PBI electrospun nanofibers displayed excellent sulfur removal, keeping sulfur in the fuel after the oxidation/adsorption below the determined limit of detection (LOD), which is 2.4 ppm S. The high level of sulfur removal displayed by imprinted PBI nanofibers was ascribed to hydrogen bonding effects, and π-π stacking between aromatic sulfone compounds and the benzimidazole ring which were confirmed by chemical modelling with density functional theory (DFT) as well as the imprinting effect. The home-made pressurized hot water extraction (PHWE) system was applied for extraction/desorption of sulfone compounds adsorbed on the PBI nanofibers at a flow rate of 1 mL/min and at 150°C with an applied pressure of 30 bars. Application of molecularly imprinted PBI nanofibers for the desulfurization of oxidized hydro-treated fuel showed potential for use in refining industries to reach ultra-low sulfur fuel level, which falls below the 10 ppm sulfur limit which is mandated by the environmental protection agency (EPA) from 2015.
- Full Text:
- Authors: Ogunlaja, Adeniyi Sunday
- Date: 2014
- Subjects: Organosulfur compounds , Organosulfur compounds -- Oxidation , Organosulfur compounds -- Absorption and adsorption , Petroleum as fuel , Catalysis , Imprinted polymers , Molecular imprinting , Nanofibers , Electrospinning
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4498 , http://hdl.handle.net/10962/d1013152
- Description: The syntheses and evaluation of oxidovanadium(IV) complexes as catalysts for the oxidation of refractory organosulfur compounds in fuels is presented. The sulfones produced from the oxidation reaction were removed from fuel oils by employing molecularly imprinted polymers (MIPs). The oxidovanadium(IV) homogeneous catalyst, [V ͥ ͮ O(sal-HBPD)], as well as its heterogeneous polymer supported derivatives, poly[V ͥ ͮ O(sal-AHBPD)] and poly[V ͥ ͮ O(allylSB-co-EGDMA)], were synthesized and fully characterized by elemental analysis, FTIR, UV-Vis, XPS, AFM, SEM, BET and single crystal XRD for [V ͥ ͮ O(sal-HBPD)]. The MIPs were also characterized by elemental analysis, FTIR, SEM, EDX and BET. The catalyzed oxidation of fuel oil model sulfur compounds, thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT), was conducted under batch and continuous flow processes at 40°C by using tert-butylhydroperoxide (t-BuOOH) as oxidant. The continuous flow oxidation process presented the highest overall conversions and very high selectivity for sulfones. Maximum oxidation conversions of 71%, 89%, 99% and 88% was achieved for TH, BT, DBT and 4,6-DMDBT respectively when poly[V ͥ ͮ O(allylSB-co-EGDMA)] was employed at a flow-rate of 1 mL/h with over 90% sulfone selectivity. The process was further applied to the oxidation of hydro-treated diesel containing 385 ± 4.6 ppm of sulfur (mainly dibenzothiophene and dibenzothiophene derivatives), and this resulted to a high sulfur oxidation yield (> 99%), thus producing polar sulfones which are extractible by polar solid phase extractants. Adsorption of the polar sulfone compounds was carried-out by employing MIPs which were fabricated through the formation of recognition sites complementary to oxidized sulfur-containing compounds (sulfones) on electrospun polybenzimidazole (PBI) nanofibers, cross-linked chitosan microspheres and electrospun chitosan nanofibers. Adsorption of benzothiophene sulfone (BTO₂), dibenzothiophene sulfone (DBTO₂) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO₂) on the various molecularly imprinted adsorbents presented a Freundlich (multi-layered) adsorption isotherm which indicated interaction of adsorbed organosulfur compounds. Maximum adsorption observed for BTO₂, DBTO₂ and 4,6-DMDBTO₂ respectively was 8.5 ± 0.6 mg/g, 7.0 ± 0.5 mg/g and 6.6 ± 0.7 mg/g when imprinted chitosan nanofibers were employed, 4.9 ± 0.5 mg/g, 4.2 ± 0.7 mg/g and 3.9 ± 0.6 mg/g on molecularly imprinted chitosan microspheres, and 28.5 ± 0.4 mg/g, 29.8 ± 2.2 mg/g and 20.1 ± 1.4 mg/g on molecularly imprinted PBI nanofibers. Application of electrospun chitosan nanofibers on oxidized hydro-treated diesel presented a sulfur removal capacity of 84%, leaving 62 ± 3.2 ppm S in the fuel, while imprinted PBI electrospun nanofibers displayed excellent sulfur removal, keeping sulfur in the fuel after the oxidation/adsorption below the determined limit of detection (LOD), which is 2.4 ppm S. The high level of sulfur removal displayed by imprinted PBI nanofibers was ascribed to hydrogen bonding effects, and π-π stacking between aromatic sulfone compounds and the benzimidazole ring which were confirmed by chemical modelling with density functional theory (DFT) as well as the imprinting effect. The home-made pressurized hot water extraction (PHWE) system was applied for extraction/desorption of sulfone compounds adsorbed on the PBI nanofibers at a flow rate of 1 mL/min and at 150°C with an applied pressure of 30 bars. Application of molecularly imprinted PBI nanofibers for the desulfurization of oxidized hydro-treated fuel showed potential for use in refining industries to reach ultra-low sulfur fuel level, which falls below the 10 ppm sulfur limit which is mandated by the environmental protection agency (EPA) from 2015.
- Full Text: