Monetary valuation of livelihoods for understanding the composition and complexity of rural households
- Dovie, Delali B K, Witkowski, Ed T F, Shackleton, Charlie M
- Authors: Dovie, Delali B K , Witkowski, Ed T F , Shackleton, Charlie M
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181346 , vital:43721 , xlink:href="https://doi.org/10.1007/s10460-004-7233-0"
- Description: There is, at present, little precise understanding of the relative contributions of the various income streams used by impoverished rural households in southern Africa. The impact of household profiles on overall income also is not well understood. There is, therefore, little consideration of these factors in national economic accounting. This paper is an attempt to reduce this gap in knowledge by reflecting on the relative contribution of agro-pastoralism, secondary woodland resources, and formal and informal cash income streams to households in the semi-arid rural village of Thorndale, Limpopo Province, South Africa. In the absence of jobs and confronted with high migrant labor, households with open access to natural resources derived more benefits from land-based livelihoods than cash income streams (i.e., 57.5 % vs. 42.5 %). Total livelihood income was valued at US$2887 per household per annum. A significant correlation between monetary values derived from crops and formal wages was established, and it was found that households with high cash incomes tended to invest more in crop production. Over 80 of households were male-headed. Of these heads of household, more than 60 were long-term migrants to urban areas, leaving household decision-making to the women. The low literacy rates of women have deprived them of paid jobs outside the area and, therefore, have increased their dependence on crops (62%) and secondary woodlands resources (60%). This was further reflected in the proportion of households in which females were the main contributors of cash income (9.7%), or joint contributors with men (24.4%). Various positive correlations were established between the number of women per household and the three land-based livelihoods. This implied that women’s total control over such activities was mostly a result of the absence of men and not a typical phenomenon. In spite of this control, it was not positively reflected in the lives of majority of the women. Households differed in their participation in livelihood activities. Household size influenced the level of production and was positively correlated with the value of secondary woodland resources and crops. The study shows the interdependence of land-based livelihood sources and the impact of household features on production and consumption. Policies that focus on livelihood options need to recognize and accommodate associated household dynamics.
- Full Text:
- Date Issued: 2005
- Authors: Dovie, Delali B K , Witkowski, Ed T F , Shackleton, Charlie M
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181346 , vital:43721 , xlink:href="https://doi.org/10.1007/s10460-004-7233-0"
- Description: There is, at present, little precise understanding of the relative contributions of the various income streams used by impoverished rural households in southern Africa. The impact of household profiles on overall income also is not well understood. There is, therefore, little consideration of these factors in national economic accounting. This paper is an attempt to reduce this gap in knowledge by reflecting on the relative contribution of agro-pastoralism, secondary woodland resources, and formal and informal cash income streams to households in the semi-arid rural village of Thorndale, Limpopo Province, South Africa. In the absence of jobs and confronted with high migrant labor, households with open access to natural resources derived more benefits from land-based livelihoods than cash income streams (i.e., 57.5 % vs. 42.5 %). Total livelihood income was valued at US$2887 per household per annum. A significant correlation between monetary values derived from crops and formal wages was established, and it was found that households with high cash incomes tended to invest more in crop production. Over 80 of households were male-headed. Of these heads of household, more than 60 were long-term migrants to urban areas, leaving household decision-making to the women. The low literacy rates of women have deprived them of paid jobs outside the area and, therefore, have increased their dependence on crops (62%) and secondary woodlands resources (60%). This was further reflected in the proportion of households in which females were the main contributors of cash income (9.7%), or joint contributors with men (24.4%). Various positive correlations were established between the number of women per household and the three land-based livelihoods. This implied that women’s total control over such activities was mostly a result of the absence of men and not a typical phenomenon. In spite of this control, it was not positively reflected in the lives of majority of the women. Households differed in their participation in livelihood activities. Household size influenced the level of production and was positively correlated with the value of secondary woodland resources and crops. The study shows the interdependence of land-based livelihood sources and the impact of household features on production and consumption. Policies that focus on livelihood options need to recognize and accommodate associated household dynamics.
- Full Text:
- Date Issued: 2005
Photochemical and photophysical properties of pentoxy-and naphthaloxy appended magnesium and zinc phthalocyanines
- Maqanda, Wesiwe, Nyokong, Tebello, Maree, David M
- Authors: Maqanda, Wesiwe , Nyokong, Tebello , Maree, David M
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289260 , vital:56613 , xlink:href="https://doi.org/10.1142/S1088424605000435"
- Description: Photochemical and photophysical measurements were conducted on pentoxy and naphthaloxy appended zinc and magnesium phthalocyanines. We describe in this paper the synthesis as well as unexpected photodegradation behavior of naphthaloxy appended magnesium phthalocyanines. General trends are described for quantum yields of photodegradation, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds.
- Full Text:
- Date Issued: 2005
- Authors: Maqanda, Wesiwe , Nyokong, Tebello , Maree, David M
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289260 , vital:56613 , xlink:href="https://doi.org/10.1142/S1088424605000435"
- Description: Photochemical and photophysical measurements were conducted on pentoxy and naphthaloxy appended zinc and magnesium phthalocyanines. We describe in this paper the synthesis as well as unexpected photodegradation behavior of naphthaloxy appended magnesium phthalocyanines. General trends are described for quantum yields of photodegradation, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds.
- Full Text:
- Date Issued: 2005
Photophysical and photochemical studies of sulphonated non-transition metal phthalocyanines in aqueous and non-aqueous media
- Ogunsipe, Abimbola, Nyokong, Tebello
- Authors: Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289271 , vital:56614 , xlink:href="https://doi.org/10.1016/j.jphotochem.2005.03.001"
- Description: The photophysical and photochemical parameters for mixed sulphonated metallophthalocyanine complexes (AlPcSmix, SiPcSmix, GePcSmix, SnPcSmix, and ZnPcSmix) are reported in phosphate buffer saline (PBS, pH 7.4), PBS containing the surfactant Triton X-100, and in dimethylsulphoxide (DMSO). The ground state spectra of SiPcSmix, GePcSmix and SnPcSmix show splitting of the Q-band in DMSO, but the fluorescence spectra have only one band, suggesting that only some components of the mixed complexes fluoresce. In general the quantum yields of fluorescence (ΦF) were smaller in DMSO compared to the aqueous solvents, while quantum yields of triplet state (ΦT) were larger in DMSO. Triplet lifetimes were much lower in aqueous solutions (compared to DMSO) due to the fact that water absorbs strongly around 1108 nm, which corresponds to the triplet energy of a metallophthalocyanine complex. The MPcSmix complexes quenched hydroquinone, and the Stern–Volmer constants follow the order: AlPcSmix > SiPcSmix > GePcSmix > ZnPcSmix > SnPcSmix which is the order of the extinction coefficients (of the low energy band for complexes with split Q-band) of these molecules. The rate constants for fluorescence, intersystem crossing, internal conversion, and photodegradation were determined from the hydroquinone quenching data.
- Full Text:
- Date Issued: 2005
- Authors: Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289271 , vital:56614 , xlink:href="https://doi.org/10.1016/j.jphotochem.2005.03.001"
- Description: The photophysical and photochemical parameters for mixed sulphonated metallophthalocyanine complexes (AlPcSmix, SiPcSmix, GePcSmix, SnPcSmix, and ZnPcSmix) are reported in phosphate buffer saline (PBS, pH 7.4), PBS containing the surfactant Triton X-100, and in dimethylsulphoxide (DMSO). The ground state spectra of SiPcSmix, GePcSmix and SnPcSmix show splitting of the Q-band in DMSO, but the fluorescence spectra have only one band, suggesting that only some components of the mixed complexes fluoresce. In general the quantum yields of fluorescence (ΦF) were smaller in DMSO compared to the aqueous solvents, while quantum yields of triplet state (ΦT) were larger in DMSO. Triplet lifetimes were much lower in aqueous solutions (compared to DMSO) due to the fact that water absorbs strongly around 1108 nm, which corresponds to the triplet energy of a metallophthalocyanine complex. The MPcSmix complexes quenched hydroquinone, and the Stern–Volmer constants follow the order: AlPcSmix > SiPcSmix > GePcSmix > ZnPcSmix > SnPcSmix which is the order of the extinction coefficients (of the low energy band for complexes with split Q-band) of these molecules. The rate constants for fluorescence, intersystem crossing, internal conversion, and photodegradation were determined from the hydroquinone quenching data.
- Full Text:
- Date Issued: 2005
Photophysical properties of a water-soluble adjacently substituted bisnaphthalophthalocyanine
- Seotsanyana-Mokhosi, Itumeleng, Nyokong, Tebello
- Authors: Seotsanyana-Mokhosi, Itumeleng , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286091 , vital:56237 , xlink:href="https://doi.org/10.1142/S1088424605000599"
- Description: Spectral properties of a water soluble metal free tetracarboxyphenoxy bisnaphthalo-phthalocyanine (3) were studied in water and organic solvents. It was found that in protic solvents, complex 3 was highly aggregated. The surfactant, Triton X100, and bovineserum albumin (BSA) do not effect disaggregation while cetyl trimethylammonium chloride (CTAC) caused the molecule to disaggregate. The fluorescence quantum yields were higher in the presence of CTAC. Studying the interaction of BSA with complex 3 using fluorometry revealed that BSA is highly quenched by the latter. A 1:1 stoichiometric binding ratio between BSA and the Pc was found. Triplet quantum yields in water containing CTAC were higher than in organic solvents.
- Full Text:
- Date Issued: 2005
- Authors: Seotsanyana-Mokhosi, Itumeleng , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286091 , vital:56237 , xlink:href="https://doi.org/10.1142/S1088424605000599"
- Description: Spectral properties of a water soluble metal free tetracarboxyphenoxy bisnaphthalo-phthalocyanine (3) were studied in water and organic solvents. It was found that in protic solvents, complex 3 was highly aggregated. The surfactant, Triton X100, and bovineserum albumin (BSA) do not effect disaggregation while cetyl trimethylammonium chloride (CTAC) caused the molecule to disaggregate. The fluorescence quantum yields were higher in the presence of CTAC. Studying the interaction of BSA with complex 3 using fluorometry revealed that BSA is highly quenched by the latter. A 1:1 stoichiometric binding ratio between BSA and the Pc was found. Triplet quantum yields in water containing CTAC were higher than in organic solvents.
- Full Text:
- Date Issued: 2005
Playing musement games: Retroduction in social research, with particular reference to indigenous knowledge in environmental and health education
- Authors: Price, Leigh
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/373763 , vital:66722 , xlink:href="https://www.ajol.info/index.php/sajee/article/view/122701"
- Description: My aim here is to introduce the concept of musement (retroduction or abduction) as an appropriate alternative to deduction and induction, both in indigenous knowledge (IK) specifically and in social science generally. As an example, I will use musement to tentatively address some of the ethical problems of using indigenous knowledge (IK) in environmental education and health education. This paper will therefore be of use both to researchers/educators wanting a discussion of retroduction, and researchers/educators wanting a discussion of indigenous knowledge epistemology and its relationship with ethics. I am arguing, from a perspective that allows a stratified reality (things can be real even if not measurable or actually present), that, we admit retroduction into our list of allowable research logics. In terms of IK, the result of accepting retroduction as a valid logic is that we allow IK to be dynamic and non-reified. It also allows a previously ignored aspect of IK, its spiritual/non-empirical beliefs, to be validated through ethical outcomes experienced in our lives, rather than through the previous criteria of empirical validity. In other words, we ask for IK: does believing in (whatever) adequately explain experience and/or provide optimistic, long term, ethical, appropriate ways of living? Thus, retroduction has the potential to allow IK to contribute to a normative ethics.
- Full Text:
- Date Issued: 2005
- Authors: Price, Leigh
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/373763 , vital:66722 , xlink:href="https://www.ajol.info/index.php/sajee/article/view/122701"
- Description: My aim here is to introduce the concept of musement (retroduction or abduction) as an appropriate alternative to deduction and induction, both in indigenous knowledge (IK) specifically and in social science generally. As an example, I will use musement to tentatively address some of the ethical problems of using indigenous knowledge (IK) in environmental education and health education. This paper will therefore be of use both to researchers/educators wanting a discussion of retroduction, and researchers/educators wanting a discussion of indigenous knowledge epistemology and its relationship with ethics. I am arguing, from a perspective that allows a stratified reality (things can be real even if not measurable or actually present), that, we admit retroduction into our list of allowable research logics. In terms of IK, the result of accepting retroduction as a valid logic is that we allow IK to be dynamic and non-reified. It also allows a previously ignored aspect of IK, its spiritual/non-empirical beliefs, to be validated through ethical outcomes experienced in our lives, rather than through the previous criteria of empirical validity. In other words, we ask for IK: does believing in (whatever) adequately explain experience and/or provide optimistic, long term, ethical, appropriate ways of living? Thus, retroduction has the potential to allow IK to contribute to a normative ethics.
- Full Text:
- Date Issued: 2005
Research on indigenous knowledge and its application: A case of wild food plants of Zimbabwe
- Authors: Shava, Soul
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/373809 , vital:66725 , xlink:href="https://www.ajol.info/index.php/sajee/article/view/122700"
- Description: Research on indigenous knowledge should go beyond documenting and interpreting it. Rather, it should stimulate inquiry into its application in present day community development and education settings. This study intends to steer indigenous knowledge research towards practical application initiatives. The study documents wild food plants of Zimbabwe, highlights some popular wild food plants, and cites some commercially marketed wild food plants and makes recommendations on the application of indigenous knowledge of wild food plants in community and educational settings.
- Full Text:
- Date Issued: 2005
- Authors: Shava, Soul
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/373809 , vital:66725 , xlink:href="https://www.ajol.info/index.php/sajee/article/view/122700"
- Description: Research on indigenous knowledge should go beyond documenting and interpreting it. Rather, it should stimulate inquiry into its application in present day community development and education settings. This study intends to steer indigenous knowledge research towards practical application initiatives. The study documents wild food plants of Zimbabwe, highlights some popular wild food plants, and cites some commercially marketed wild food plants and makes recommendations on the application of indigenous knowledge of wild food plants in community and educational settings.
- Full Text:
- Date Issued: 2005
Social epistemology and its politically correct words: Avoiding absolutism, relativism, consensualism, and vulgar pragmatism
- Authors: Price, Leigh
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/373833 , vital:66727 , xlink:href="https://hdl.handle.net/10520/ejc-cristal-v10-n1-a7"
- Description: Where social epistemology has been applied in environmental education research, certain words have come to be associated with it, such as, "social," "contextualized," "strategic," "political," "pragmatic," "democratic," and "participatory." In this paper, I first suggest interpretations of these words that potentially avoid absolutism, relativism, consensualism, and vulgar pragmatism. I then identify interpretations that succumb to these problems. To support my argument, I draw on Peircean scholars, critical realist scholars, and scholars who rely on a tranche of metaphor that evoke images of connections, partnerships, webs, and rhizomes. These writers suggest a social epistemology in which in which relationships, not objects, are primary.
- Full Text:
- Date Issued: 2005
- Authors: Price, Leigh
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/373833 , vital:66727 , xlink:href="https://hdl.handle.net/10520/ejc-cristal-v10-n1-a7"
- Description: Where social epistemology has been applied in environmental education research, certain words have come to be associated with it, such as, "social," "contextualized," "strategic," "political," "pragmatic," "democratic," and "participatory." In this paper, I first suggest interpretations of these words that potentially avoid absolutism, relativism, consensualism, and vulgar pragmatism. I then identify interpretations that succumb to these problems. To support my argument, I draw on Peircean scholars, critical realist scholars, and scholars who rely on a tranche of metaphor that evoke images of connections, partnerships, webs, and rhizomes. These writers suggest a social epistemology in which in which relationships, not objects, are primary.
- Full Text:
- Date Issued: 2005
Surface electrochemistry of iron phthalocyanine axially ligated to 4-mercaptopyridine self-assembled monolayers at gold electrode
- Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289282 , vital:56615 , xlink:href="https://doi.org/10.1016/j.jelechem.2005.02.018"
- Description: Surface electrochemical behaviour of a self-immobilised iron phthalocyanine (FePc) ultrathin film, via axial ligation reaction, onto a preformed 4-mercaptopyridine self-assembled monolayer on gold electrode has been described. Electrochemical evidence for the sensor clearly suggested surface-confined, flat “umbrella”-oriented and densely-packed monolayer film structure. The proposed electrochemical sensor exhibited good catalytic activity towards the oxidation of thiocyanate in pH 4.0 medium over a linear range of three decades of concentration (ca. 10−6–10−3 mol dm−3) with a detection limit in the order of ∼10−7 mol dm−3. The sensor exhibited useful potential for the analysis of thiocyanate in human urine and saliva samples. The advantageous properties of this type of electrode as a sensor for thiocyanate lie in its ease of fabrication, excellent catalytic activity, stability, sensitivity and simplicity.
- Full Text:
- Date Issued: 2005
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289282 , vital:56615 , xlink:href="https://doi.org/10.1016/j.jelechem.2005.02.018"
- Description: Surface electrochemical behaviour of a self-immobilised iron phthalocyanine (FePc) ultrathin film, via axial ligation reaction, onto a preformed 4-mercaptopyridine self-assembled monolayer on gold electrode has been described. Electrochemical evidence for the sensor clearly suggested surface-confined, flat “umbrella”-oriented and densely-packed monolayer film structure. The proposed electrochemical sensor exhibited good catalytic activity towards the oxidation of thiocyanate in pH 4.0 medium over a linear range of three decades of concentration (ca. 10−6–10−3 mol dm−3) with a detection limit in the order of ∼10−7 mol dm−3. The sensor exhibited useful potential for the analysis of thiocyanate in human urine and saliva samples. The advantageous properties of this type of electrode as a sensor for thiocyanate lie in its ease of fabrication, excellent catalytic activity, stability, sensitivity and simplicity.
- Full Text:
- Date Issued: 2005
Synthesis and photophysical properties of a covalently linked porphyrin-phthalocyanine conjugate
- Zhao, Zhixin, Ogunsipe, Abimbola O, Maree, M David, Nyokong, Tebello
- Authors: Zhao, Zhixin , Ogunsipe, Abimbola O , Maree, M David , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300358 , vital:57922 , xlink:href="https://doi.org/10.1142/S1088424605000253"
- Description: The synthesis of a phthalocyanine-porphyrin heteropentamer (zinc(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin)) zinc(II) phthalocyanine, (ZnPc-(ZnTPP)4), containing four units of zinc tetraphenylporphyrin linked to a central zinc phthalocyanine macrocycle via an ether linkage is reported. The photophysical parameters of the pentamer are reported in toluene and dimethyl sulfoxide (DMSO). The observed differences in the fluorescence behavior of the pentamer in the two solvents is explained in terms of emission from different states; charge transfer state in DMSO and locally excited state in toluene. The rate constants for fluorescence, intersystem crossing, internal conversion, and of charge and energy transfer are reported for the pentamer. Quantum yields for fluorescence, internal conversion, triplet state and of charge and energy transfer are also reported for the pentamer, ZnPc-(ZnTPP)4 and the mixture of ZnPc and ZnTPP. The latter two parameters are higher in the pentamer compared to a mixture containing ZnPc and ZnTPP.
- Full Text:
- Date Issued: 2005
- Authors: Zhao, Zhixin , Ogunsipe, Abimbola O , Maree, M David , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300358 , vital:57922 , xlink:href="https://doi.org/10.1142/S1088424605000253"
- Description: The synthesis of a phthalocyanine-porphyrin heteropentamer (zinc(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin)) zinc(II) phthalocyanine, (ZnPc-(ZnTPP)4), containing four units of zinc tetraphenylporphyrin linked to a central zinc phthalocyanine macrocycle via an ether linkage is reported. The photophysical parameters of the pentamer are reported in toluene and dimethyl sulfoxide (DMSO). The observed differences in the fluorescence behavior of the pentamer in the two solvents is explained in terms of emission from different states; charge transfer state in DMSO and locally excited state in toluene. The rate constants for fluorescence, intersystem crossing, internal conversion, and of charge and energy transfer are reported for the pentamer. Quantum yields for fluorescence, internal conversion, triplet state and of charge and energy transfer are also reported for the pentamer, ZnPc-(ZnTPP)4 and the mixture of ZnPc and ZnTPP. The latter two parameters are higher in the pentamer compared to a mixture containing ZnPc and ZnTPP.
- Full Text:
- Date Issued: 2005
Synthesis, electrochemical and electrocatalytic behaviour of thiophene-appended cobalt, manganese and zinc phthalocyanine complexes
- Obirai, Joseph, Nyokong, Tebello
- Authors: Obirai, Joseph , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286103 , vital:56238 , xlink:href="https://doi.org/10.1016/j.electacta.2005.03.024"
- Description: This work reports on the syntheses of new thiophene tetra substituted cobalt, manganese and zinc phthalocyanine (CoTETPc, (Cl)MnTETPc and ZnTETPc) complexes. The redox processes due to the thiophene substituent on the ring of the metallophthalocyanines (MPcs) were observed, in addition to Pc ring and metal (for Co and Mn complexes) based redox activity. The electrocatalytic activity of the CoTETPc complex adsorbed on glassy carbon electrode (GCE) by drop/dry-thermal annealing was investigated using L-cysteine. The modified electrode was stable to repetitive use without any signs of deactivation by oxidation products and was used to determine L-cysteine at concentrations between 0.0015 and 1 mM in pH 4 aqueous conditions.
- Full Text:
- Date Issued: 2005
- Authors: Obirai, Joseph , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286103 , vital:56238 , xlink:href="https://doi.org/10.1016/j.electacta.2005.03.024"
- Description: This work reports on the syntheses of new thiophene tetra substituted cobalt, manganese and zinc phthalocyanine (CoTETPc, (Cl)MnTETPc and ZnTETPc) complexes. The redox processes due to the thiophene substituent on the ring of the metallophthalocyanines (MPcs) were observed, in addition to Pc ring and metal (for Co and Mn complexes) based redox activity. The electrocatalytic activity of the CoTETPc complex adsorbed on glassy carbon electrode (GCE) by drop/dry-thermal annealing was investigated using L-cysteine. The modified electrode was stable to repetitive use without any signs of deactivation by oxidation products and was used to determine L-cysteine at concentrations between 0.0015 and 1 mM in pH 4 aqueous conditions.
- Full Text:
- Date Issued: 2005
Synthesis, photophysicochemical studies of adjacently tetrasubstituted binaphthalo-phthalocyanines
- Seotsanyana-Mokhosi, Itumeleng, Chen, Ji-Yao, Nyokong, Tebello
- Authors: Seotsanyana-Mokhosi, Itumeleng , Chen, Ji-Yao , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289294 , vital:56616 , xlink:href="https://doi.org/10.1142/S108842460500040X"
- Description: Adjacent binaphthalo-phthalocyanines tetra-substituted with phenoxy (4a), 4-carboxyphenoxy (4b) and 4-t-butylphenoxy (4c) groups, as well as the di-substituted 4-carboxyphenoxy (5b) have been synthesized and characterized. The photophysical and photochemical behavior of 4a-c, were compared with those of the corresponding di-substituted derivatives, (5a-c). The secondary substituents on the phenoxy ring have an influence on the aggregation of the molecules and hence on their photophysical properties. All of the complexes exhibit a relatively good conversion of energy from the triplet-excited state to the singlet oxygen. The less aggregated molecule (4c), has the highest singlet oxygen quantum yield. For all the molecules, fluorescence yields are low and they all have relatively shorter triplet lifetimes compared with the unsubstituted zinc phthalocyanine. Increasing the number of ring substituents on these rigid MPc complexes (from complexes 5 to 4) showed a general increase in the triplet state lifetimes and singlet oxygen quantum yields, and a decrease in stability.
- Full Text:
- Date Issued: 2005
- Authors: Seotsanyana-Mokhosi, Itumeleng , Chen, Ji-Yao , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289294 , vital:56616 , xlink:href="https://doi.org/10.1142/S108842460500040X"
- Description: Adjacent binaphthalo-phthalocyanines tetra-substituted with phenoxy (4a), 4-carboxyphenoxy (4b) and 4-t-butylphenoxy (4c) groups, as well as the di-substituted 4-carboxyphenoxy (5b) have been synthesized and characterized. The photophysical and photochemical behavior of 4a-c, were compared with those of the corresponding di-substituted derivatives, (5a-c). The secondary substituents on the phenoxy ring have an influence on the aggregation of the molecules and hence on their photophysical properties. All of the complexes exhibit a relatively good conversion of energy from the triplet-excited state to the singlet oxygen. The less aggregated molecule (4c), has the highest singlet oxygen quantum yield. For all the molecules, fluorescence yields are low and they all have relatively shorter triplet lifetimes compared with the unsubstituted zinc phthalocyanine. Increasing the number of ring substituents on these rigid MPc complexes (from complexes 5 to 4) showed a general increase in the triplet state lifetimes and singlet oxygen quantum yields, and a decrease in stability.
- Full Text:
- Date Issued: 2005
The contribution and direct-use value of livestock to rural livelihoods in the Sand River catchment, South Africa
- Shackleton, Charlie M, Shackleton, Sheona E, Netshiluvhi, T R, Mathabela, F R
- Authors: Shackleton, Charlie M , Shackleton, Sheona E , Netshiluvhi, T R , Mathabela, F R
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181335 , vital:43720 , xlink:href="https://doi.org/10.2989/10220110509485870"
- Description: The productive functions of livestock ownership in communal areas are multipurpose in character, comprising a mix of stock types and a range of goods and services used. When all these multiple uses are accounted for, the cash and direct-use returns of livestock in communal areas can be comparable to commercial systems, although temporally and spatially variable. Yet previous work has generally excluded small stock from such analyses, as well as benefits and costs to non-owning households. This paper presents empirical results of a study in the Sand River catchment, assessing the benefits and costs accruing to owners and non-owners for both cattle and goats within a livelihoods analysis framework. Results indicate that cattle are used for a greater variety of goods and services than are goats. The savings value represented the most important function, followed by milk and then manure. Even if savings value was excluded, cattle ownership made a significant contribution to local livelihoods. Goats also provided a net positive benefit, represented largely by the savings value, followed by meat and cash sales. Non-owners also benefited through donations of manure, milk, draught and meat for free, or at a cheaper rate than alternatives. The majority of non-owners aspired to livestock ownership, although the risk of theft of animals was of growing concern. Averaged across the whole catchment, the net value of goods and services from livestock was just over R400 per hectare, with an annual return to capital of 36%. Cattle contributed the bulk of the value by virtue of their greater numbers and larger size, but on a per kilogramme basis goats provided higher value. Many of the goods and services obtained from livestock were not enumerated in regional or national economic statistics.
- Full Text:
- Date Issued: 2005
- Authors: Shackleton, Charlie M , Shackleton, Sheona E , Netshiluvhi, T R , Mathabela, F R
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181335 , vital:43720 , xlink:href="https://doi.org/10.2989/10220110509485870"
- Description: The productive functions of livestock ownership in communal areas are multipurpose in character, comprising a mix of stock types and a range of goods and services used. When all these multiple uses are accounted for, the cash and direct-use returns of livestock in communal areas can be comparable to commercial systems, although temporally and spatially variable. Yet previous work has generally excluded small stock from such analyses, as well as benefits and costs to non-owning households. This paper presents empirical results of a study in the Sand River catchment, assessing the benefits and costs accruing to owners and non-owners for both cattle and goats within a livelihoods analysis framework. Results indicate that cattle are used for a greater variety of goods and services than are goats. The savings value represented the most important function, followed by milk and then manure. Even if savings value was excluded, cattle ownership made a significant contribution to local livelihoods. Goats also provided a net positive benefit, represented largely by the savings value, followed by meat and cash sales. Non-owners also benefited through donations of manure, milk, draught and meat for free, or at a cheaper rate than alternatives. The majority of non-owners aspired to livestock ownership, although the risk of theft of animals was of growing concern. Averaged across the whole catchment, the net value of goods and services from livestock was just over R400 per hectare, with an annual return to capital of 36%. Cattle contributed the bulk of the value by virtue of their greater numbers and larger size, but on a per kilogramme basis goats provided higher value. Many of the goods and services obtained from livestock were not enumerated in regional or national economic statistics.
- Full Text:
- Date Issued: 2005
The effect of structure on the electrochemical properties of 14 marine pyrroloquinoline metabolites
- Antunes, Edith M, Maree, Suzanne E, Nyokong, Tebello, Davies-Coleman, Michael T, Maree, M David
- Authors: Antunes, Edith M , Maree, Suzanne E , Nyokong, Tebello , Davies-Coleman, Michael T , Maree, M David
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286126 , vital:56242 , xlink:href="https://doi.org/10.3184/030823405775146915"
- Description: The electrochemical properties of 14 structurally related pyrroloquinoline metabolites (compounds 1–14) isolated from marine sponges were studied in pH-varied experiments using cyclic and square wave voltammetry. In general both substitution patterns and pH were observed to influence the reduction potentials of these molecules.
- Full Text:
- Date Issued: 2005
- Authors: Antunes, Edith M , Maree, Suzanne E , Nyokong, Tebello , Davies-Coleman, Michael T , Maree, M David
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286126 , vital:56242 , xlink:href="https://doi.org/10.3184/030823405775146915"
- Description: The electrochemical properties of 14 structurally related pyrroloquinoline metabolites (compounds 1–14) isolated from marine sponges were studied in pH-varied experiments using cyclic and square wave voltammetry. In general both substitution patterns and pH were observed to influence the reduction potentials of these molecules.
- Full Text:
- Date Issued: 2005
Towards a better grasp of what matters in view of ‘the posts’
- O'Donoghue, Rob B, Lotz-Sisitka, Heila
- Authors: O'Donoghue, Rob B , Lotz-Sisitka, Heila
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/182693 , vital:43854 , xlink:href="https://doi.org/10.1080/13504620500169593"
- Description: This response to McKenzie suggests that the issues of representivity, legitimacy and politics, inscribed within an institutional continuism characteristic of modernity within the McKenzie discourse, could well be recast within a reflexive view informed by insights derived with developing social theory. It briefly overviews the struggle for human agency that played out within the deconstructive engagements of the posts and probes how perspectives in social theory are opening the way for a break with features of environmental education as an institutional field. The review points to a reconstituting of the idea of environmental education research from scholastic field of/for environmental awareness and sustainable development, to a reflexive engagement within processes of social reproduction and reorientation in a changing world. A shift such as this would constitute a subtle change in a developing field of research, to situated design decisions of reflexive engagement (research) in social fields constituted within developing cultural contexts of risk.
- Full Text:
- Date Issued: 2005
- Authors: O'Donoghue, Rob B , Lotz-Sisitka, Heila
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/182693 , vital:43854 , xlink:href="https://doi.org/10.1080/13504620500169593"
- Description: This response to McKenzie suggests that the issues of representivity, legitimacy and politics, inscribed within an institutional continuism characteristic of modernity within the McKenzie discourse, could well be recast within a reflexive view informed by insights derived with developing social theory. It briefly overviews the struggle for human agency that played out within the deconstructive engagements of the posts and probes how perspectives in social theory are opening the way for a break with features of environmental education as an institutional field. The review points to a reconstituting of the idea of environmental education research from scholastic field of/for environmental awareness and sustainable development, to a reflexive engagement within processes of social reproduction and reorientation in a changing world. A shift such as this would constitute a subtle change in a developing field of research, to situated design decisions of reflexive engagement (research) in social fields constituted within developing cultural contexts of risk.
- Full Text:
- Date Issued: 2005
Reactor development and process optimisation for the bioremediation of phenolic wastewaters by trametes species
- Authors: Ryan, Daniel Reginald
- Date: 2004-04
- Subjects: Uncatalogued
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/191487 , vital:45103
- Description: In many service industries, the source of a company’s value has shifted from capital to knowledge and ideas, the quality of which is dependent on its employees (Wooldridge, 2006). In fact, human resources can be considered part of factor conditions which can positively impact on a firm’s competitive context. This impact can ultimately translate into improved financial results (Porter and Kramer, 2002). There is therefore a growing interest in ways to attract and retain talent. According to the managers of many big companies, well communicated corporate responsibility practices can improve staff attraction as well as retention rates by improving morale (CSRwire, 2002). To explore this, a small, creative company in Johannesburg which engages in charity work was selected as a case study, with the goal being to understand whether their culture of good deeds has a positive impact on staff wellbeing. While the owner of the company actively attempts to make the company an enjoyable place to work at, he appears to have initiated the philanthropic activities in a true spirit of giving, rather than with the motive of engaging staff in order to make more money. Nevertheless, the researcher’s investigative stance is that of an enlightened egoist, and the study focuses on the business case of giving being beneficial to the giver (ultimately the company) in the long term, as well as to the recipient. While the danger of suggesting that philanthropy could be instrumentalised is acknowledged (Morton, 2004), the investigation explores the possibility because such evidence could persuade other companies to become more socially concerned. Through a qualitative approach involving interviews, observation and analysis of video footage, it becomes apparent that there is clearly value for the staff in the charity work they do. Unfortunately the multiple initiatives undertaken to keep staff morale high at the company make it impossible to establish a clear link between the philanthropy and overall wellbeing, but as the study was conducted in the phenomenological paradigm the main concern was with understanding the experience of participants. However, an unexpected finding was that the employees derive great satisfaction from using their professional skills for charity work rather than just donating money to the charity. They feel that their skills uniquely position them to make significant changes to the lives of others, which gives them a sense of pride and achievement that they don’t necessarily experience in their ordinary activities at work. On the basis of this, it is recommended that companies look to involve staff with projects that require their specific expertise when evaluating philanthropic initiatives. , Thesis (PhD) -- Faculty of Science, Biochemistry, Microbiology and Biotechnology, 2004
- Full Text:
- Date Issued: 2004-04
- Authors: Ryan, Daniel Reginald
- Date: 2004-04
- Subjects: Uncatalogued
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/191487 , vital:45103
- Description: In many service industries, the source of a company’s value has shifted from capital to knowledge and ideas, the quality of which is dependent on its employees (Wooldridge, 2006). In fact, human resources can be considered part of factor conditions which can positively impact on a firm’s competitive context. This impact can ultimately translate into improved financial results (Porter and Kramer, 2002). There is therefore a growing interest in ways to attract and retain talent. According to the managers of many big companies, well communicated corporate responsibility practices can improve staff attraction as well as retention rates by improving morale (CSRwire, 2002). To explore this, a small, creative company in Johannesburg which engages in charity work was selected as a case study, with the goal being to understand whether their culture of good deeds has a positive impact on staff wellbeing. While the owner of the company actively attempts to make the company an enjoyable place to work at, he appears to have initiated the philanthropic activities in a true spirit of giving, rather than with the motive of engaging staff in order to make more money. Nevertheless, the researcher’s investigative stance is that of an enlightened egoist, and the study focuses on the business case of giving being beneficial to the giver (ultimately the company) in the long term, as well as to the recipient. While the danger of suggesting that philanthropy could be instrumentalised is acknowledged (Morton, 2004), the investigation explores the possibility because such evidence could persuade other companies to become more socially concerned. Through a qualitative approach involving interviews, observation and analysis of video footage, it becomes apparent that there is clearly value for the staff in the charity work they do. Unfortunately the multiple initiatives undertaken to keep staff morale high at the company make it impossible to establish a clear link between the philanthropy and overall wellbeing, but as the study was conducted in the phenomenological paradigm the main concern was with understanding the experience of participants. However, an unexpected finding was that the employees derive great satisfaction from using their professional skills for charity work rather than just donating money to the charity. They feel that their skills uniquely position them to make significant changes to the lives of others, which gives them a sense of pride and achievement that they don’t necessarily experience in their ordinary activities at work. On the basis of this, it is recommended that companies look to involve staff with projects that require their specific expertise when evaluating philanthropic initiatives. , Thesis (PhD) -- Faculty of Science, Biochemistry, Microbiology and Biotechnology, 2004
- Full Text:
- Date Issued: 2004-04
The depositional history and evaluation of two late quaternary, diamondiferous pocket beaches, south-western Namibia
- Authors: Milad, Micael George
- Date: 2004-03
- Subjects: Uncatalogued
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/420934 , vital:71795
- Description: The two Late Quaternary, diamondiferous pocket beach deposits studied here are situated along a 10 km stretch of the storm-dominated, Atlantic coastline of the Sperrgebiet, south-western Namibia. The pocket beaches are approximately 130 km north of the Orange River mouth, which is widely accepted as a long-lived point source for diamonds sourced from the interior of southern Africa. A total of fourteen pocket beach deposits were recently evaluated in this area, but only two of these, namely Site 2 (to the south) and Site 3 (to the north), are considered here. The main diamondbearing horizons are beach gravels, which occur within, and form part of, the pocket beach sequences. The beach gravels are mostly blanketed by sand overburden, meaning that exposures available for study were limited, and much reliance was placed on borehole logging and observations of evaluation sample tailings. The main aims are to unravel the depositional history of the pocket beach sequences, identify the controls on diamond mineralisation in the beach gravels, and critically examine two different methods of estimating average diamond size for the deposits. In pursuit of these aims, sedimentological characteristics of the unconsolidated pocket beach deposits were recorded using small diameter drill holes, hydraulic grab bulk samples, trench exposures and surface outcrops. The surface geology, geomorphology and modern wave patterns were mapped using high-resolution, Airborne Laser Survey imagery coupled with extensive field checking. Three-dimensional geological modeling software was used to gain insight into the subsurface morphology of the deposits. Fossil shell samples were used to aid interpretation of ancient depositional environments and to date parts of the pocket beach sequences. Variations in diamond concentration and the size of diamonds were recorded using bulk samples, some of which were taken from a trench, but most of which were excavated using a hydraulic grab tool called the GB50. Finally, by using diamond size data from Site 3, sample data from diamondiferous beach gravels to the south of the study area and sample campaign simulations, two alternative methods of evaluating average diamond size in marine gravel deposits were appraised.The pocket beach sequences occur within north-south trending valleys of a major deflation basin and are separated from one another by rocky headlands. The ridge-and-valley topography of the deflation basin has resulted from differential erosion of Late Proterozoic basement rock units, alternating layers of which differ greatly in their resistance to the long-lived, local denudationalprocesses. On the basis of the stratigraphic information collected from the unconsolidated pocket beach valley fills, interpreted within the context of global, Late Pleistocene sea level records, the following depositional history is deduced : a) Deposition of sheetflood gravels by ephemeral streams, activated during a regressive phase. b) Transgression, culminating in the deposition of a gravel beach, representing a sea level highstand of +4 metres above mean sea level (mamsl) at between 120 000 and 130 000 BP. c)A regressive phase, resulting in deflation of former valley fills to the bedrock valley floor and accompanied by re-activation of ephemeral stream activity to form sheetflood deposits; this represents a protracted period of subaerial exposure of the +4 m gravel beach deposit. d) Deposition of a great volume of sediment in the valleys during the latter stages of the transgression from the Last Glacial Maximum (LGM). The sequence generated during this phase, which started at ca. 9 000 BP, contains : i) pan/coastal sabkha sediments, ii) shallow, sheltered bay sediments, iii) back-barrier lagoonal sediments, iv) a gravel beach deposit representing a sea level stillstand at -5 mamsl, laid down between 7 600 and 5 600 BP, v) another gravel beach deposit representing the well-known Middle Holocene sea level highstand at +2 to +3 mamsl, laid down at ca. 5 000 BP, and which terminated the transgression from the LGM. e) A minor regression to the current sea level, accompanied by progradation of the shoreline to its current position. This progradational marine unit consists almost entirely of sand and grit, reflecting the lack of gravel supply to this part of the coastline in the most recent past. f) Deposition of modern coastal dunes, which cap the pocket beach sequence and are the youngest sediments in the study area. Using trench and hydraulic grab evaluation sample results, in combination with analysis of wave patterns and field observations, the following local controls on the density distribution (ie. concentration) and size distribution of diamonds in the gravel beach deposits (+4, -5 and +2 to +3 mamsl stands) are recognised: a) Gravel beach depositional processes, which are responsible for clast sorting on the beach, have influenced the density and size distribution of diamonds. The infill zone, or beach toe, favours maximum diamond concentration while diamond size decreases from the imbricate zone (intertidal) to the infill zone (subtidal). b) Wave energy is identified as the dominant local control on diamond size distribution, but has also influenced diamond concentration to a limited degree. Larger diamonds are intimately associated with coarser beach gravels, both of which are a reflection of increased wave energy. Higher concentrations of diamonds are sometimes associated with zones of coarser gravel and therefore greater wave energy. c) The time of deposition of the host gravel beach is seen to be the dominant controlling factor with respect to diamond concentration. This is seen as evidence of significant temporal variation in the availability of diamonds in the littoral evironment. A significant reduction (20%) in average diamond size from Site 2 to Site 3, over a distance of only 6 km, is evident. The following were identified as reasons for this reduction in diamond size : a) Longshore sorting processes, of which the long-lived northerly littoral drift is a key part, are known to have played a role in the diminution of diamond size northwards from the Orange River mouth point source. However, it is believed that this can only partly account for the observed 20% reduction in diamond size. b) Input of sediment and smaller diamonds at Site 3, reworked out of an older, Eocene-aged marine succession in the hinterland, is recognised as a possible additional reason for the large reduction in diamond size from Site 2 to Site 3. It is also speculated that the large size of the pocket beach at Site 3, relative to Site 2, may have resulted in lower average wave energy at Site 3, with consequent reduced average diamond size. Diamond size in the beach gravels of Site 3, as well as in beach gravels elsewhere in the Sperrgebiet, is seen to be lognormally-distributed within geologically homogeneous zones. In theory, lognormal mean estimators represent the best method of estimating average diamond size in such cases, whereas the arithmetic mean estimator has the tendency to overestimate when large outlier values occur. Lognormal mean estimators have the added benefit of providing for the calculation of confidence limits, which are becoming increasingly more important as financial lending institutions insist on better quantification of the risk involved in resource estimates. Sample campaign simulations demonstrate, for the kinds of diamond size-frequency distributions typical of beach gravel deposits at Site 3, that there is no significant improvement in the accuracy of average diamond size estimates when lognormal mean estimators are used instead of the arithmetic mean estimator. This is because the variance (a ) of the diamond populations is low, and large outlier values are extremely unlikely to occur. However, simulation of a diamond population with high variance, drawn from a sample of beach gravels near the Orange River mouth, shows that lognormal estimators produce significantly more accurate results when a is large. Since individual diamond weights were not recorded during evaluation sampling of Site 3, numerical solution of lognormal estimators is not possible, and these would need to be solved using a less accurate graphical method. It is therefore recommended that individual diamond weights are recorded in future sampling campaigns, allowing for the use of lognormal mean estimators, and the calculation of confidence limits for average diamond size estimates. , Thesis (MSc) -- Science, Geology, 2004
- Full Text:
- Date Issued: 2004-03
- Authors: Milad, Micael George
- Date: 2004-03
- Subjects: Uncatalogued
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/420934 , vital:71795
- Description: The two Late Quaternary, diamondiferous pocket beach deposits studied here are situated along a 10 km stretch of the storm-dominated, Atlantic coastline of the Sperrgebiet, south-western Namibia. The pocket beaches are approximately 130 km north of the Orange River mouth, which is widely accepted as a long-lived point source for diamonds sourced from the interior of southern Africa. A total of fourteen pocket beach deposits were recently evaluated in this area, but only two of these, namely Site 2 (to the south) and Site 3 (to the north), are considered here. The main diamondbearing horizons are beach gravels, which occur within, and form part of, the pocket beach sequences. The beach gravels are mostly blanketed by sand overburden, meaning that exposures available for study were limited, and much reliance was placed on borehole logging and observations of evaluation sample tailings. The main aims are to unravel the depositional history of the pocket beach sequences, identify the controls on diamond mineralisation in the beach gravels, and critically examine two different methods of estimating average diamond size for the deposits. In pursuit of these aims, sedimentological characteristics of the unconsolidated pocket beach deposits were recorded using small diameter drill holes, hydraulic grab bulk samples, trench exposures and surface outcrops. The surface geology, geomorphology and modern wave patterns were mapped using high-resolution, Airborne Laser Survey imagery coupled with extensive field checking. Three-dimensional geological modeling software was used to gain insight into the subsurface morphology of the deposits. Fossil shell samples were used to aid interpretation of ancient depositional environments and to date parts of the pocket beach sequences. Variations in diamond concentration and the size of diamonds were recorded using bulk samples, some of which were taken from a trench, but most of which were excavated using a hydraulic grab tool called the GB50. Finally, by using diamond size data from Site 3, sample data from diamondiferous beach gravels to the south of the study area and sample campaign simulations, two alternative methods of evaluating average diamond size in marine gravel deposits were appraised.The pocket beach sequences occur within north-south trending valleys of a major deflation basin and are separated from one another by rocky headlands. The ridge-and-valley topography of the deflation basin has resulted from differential erosion of Late Proterozoic basement rock units, alternating layers of which differ greatly in their resistance to the long-lived, local denudationalprocesses. On the basis of the stratigraphic information collected from the unconsolidated pocket beach valley fills, interpreted within the context of global, Late Pleistocene sea level records, the following depositional history is deduced : a) Deposition of sheetflood gravels by ephemeral streams, activated during a regressive phase. b) Transgression, culminating in the deposition of a gravel beach, representing a sea level highstand of +4 metres above mean sea level (mamsl) at between 120 000 and 130 000 BP. c)A regressive phase, resulting in deflation of former valley fills to the bedrock valley floor and accompanied by re-activation of ephemeral stream activity to form sheetflood deposits; this represents a protracted period of subaerial exposure of the +4 m gravel beach deposit. d) Deposition of a great volume of sediment in the valleys during the latter stages of the transgression from the Last Glacial Maximum (LGM). The sequence generated during this phase, which started at ca. 9 000 BP, contains : i) pan/coastal sabkha sediments, ii) shallow, sheltered bay sediments, iii) back-barrier lagoonal sediments, iv) a gravel beach deposit representing a sea level stillstand at -5 mamsl, laid down between 7 600 and 5 600 BP, v) another gravel beach deposit representing the well-known Middle Holocene sea level highstand at +2 to +3 mamsl, laid down at ca. 5 000 BP, and which terminated the transgression from the LGM. e) A minor regression to the current sea level, accompanied by progradation of the shoreline to its current position. This progradational marine unit consists almost entirely of sand and grit, reflecting the lack of gravel supply to this part of the coastline in the most recent past. f) Deposition of modern coastal dunes, which cap the pocket beach sequence and are the youngest sediments in the study area. Using trench and hydraulic grab evaluation sample results, in combination with analysis of wave patterns and field observations, the following local controls on the density distribution (ie. concentration) and size distribution of diamonds in the gravel beach deposits (+4, -5 and +2 to +3 mamsl stands) are recognised: a) Gravel beach depositional processes, which are responsible for clast sorting on the beach, have influenced the density and size distribution of diamonds. The infill zone, or beach toe, favours maximum diamond concentration while diamond size decreases from the imbricate zone (intertidal) to the infill zone (subtidal). b) Wave energy is identified as the dominant local control on diamond size distribution, but has also influenced diamond concentration to a limited degree. Larger diamonds are intimately associated with coarser beach gravels, both of which are a reflection of increased wave energy. Higher concentrations of diamonds are sometimes associated with zones of coarser gravel and therefore greater wave energy. c) The time of deposition of the host gravel beach is seen to be the dominant controlling factor with respect to diamond concentration. This is seen as evidence of significant temporal variation in the availability of diamonds in the littoral evironment. A significant reduction (20%) in average diamond size from Site 2 to Site 3, over a distance of only 6 km, is evident. The following were identified as reasons for this reduction in diamond size : a) Longshore sorting processes, of which the long-lived northerly littoral drift is a key part, are known to have played a role in the diminution of diamond size northwards from the Orange River mouth point source. However, it is believed that this can only partly account for the observed 20% reduction in diamond size. b) Input of sediment and smaller diamonds at Site 3, reworked out of an older, Eocene-aged marine succession in the hinterland, is recognised as a possible additional reason for the large reduction in diamond size from Site 2 to Site 3. It is also speculated that the large size of the pocket beach at Site 3, relative to Site 2, may have resulted in lower average wave energy at Site 3, with consequent reduced average diamond size. Diamond size in the beach gravels of Site 3, as well as in beach gravels elsewhere in the Sperrgebiet, is seen to be lognormally-distributed within geologically homogeneous zones. In theory, lognormal mean estimators represent the best method of estimating average diamond size in such cases, whereas the arithmetic mean estimator has the tendency to overestimate when large outlier values occur. Lognormal mean estimators have the added benefit of providing for the calculation of confidence limits, which are becoming increasingly more important as financial lending institutions insist on better quantification of the risk involved in resource estimates. Sample campaign simulations demonstrate, for the kinds of diamond size-frequency distributions typical of beach gravel deposits at Site 3, that there is no significant improvement in the accuracy of average diamond size estimates when lognormal mean estimators are used instead of the arithmetic mean estimator. This is because the variance (a ) of the diamond populations is low, and large outlier values are extremely unlikely to occur. However, simulation of a diamond population with high variance, drawn from a sample of beach gravels near the Orange River mouth, shows that lognormal estimators produce significantly more accurate results when a is large. Since individual diamond weights were not recorded during evaluation sampling of Site 3, numerical solution of lognormal estimators is not possible, and these would need to be solved using a less accurate graphical method. It is therefore recommended that individual diamond weights are recorded in future sampling campaigns, allowing for the use of lognormal mean estimators, and the calculation of confidence limits for average diamond size estimates. , Thesis (MSc) -- Science, Geology, 2004
- Full Text:
- Date Issued: 2004-03
Catalytic activity of iron and cobalt phthalocyanine complexes towards the oxidation of cyclohexene using tert-butylhydroperoxide and chloroperoxybenzoic acid
- Sehlotho, Nthapo, Nyokong, Tebello
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290257 , vital:56729 , xlink:href="https://doi.org/10.1016/j.molcata.2003.08.014"
- Description: Cyclohexene oxidation using tert-butylhydroperoxide (TBHP) or chloroperoxybenzoic acid (CPBA) in the presence of iron(II) polychlorophthalocyanine (Cl16PcFe), iron(II) phthalocyanine (PcFe) and cobalt(II) phthalocyanine (PcCo), results in the formation of the following products: cyclohexene oxide, 2-cyclohexene-1-ol and 2-cyclohexene-1-one. Adipic acid was also formed after long reaction times. The selectivity for 2-cyclohexene-1-one is favoured when Cl16PcFe or PcCo catalysts are employed, while PcFe is selective towards the formation of 2-cyclohexene-1-ol. The Cl16PcFe catalyst is transformed into a μ-oxo dimer (Cl16PcFeIIIOIIIFePcCl16) during the oxidation process. The catalytic process using the unsubstituted PcCoII and PcFeII catalysts involved PcMIII species as an intermediate. The active form of the Cl16PcFe catalyst was stable to degradation in that it was still active even after 4 weeks of continued catalysis.
- Full Text:
- Date Issued: 2004
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290257 , vital:56729 , xlink:href="https://doi.org/10.1016/j.molcata.2003.08.014"
- Description: Cyclohexene oxidation using tert-butylhydroperoxide (TBHP) or chloroperoxybenzoic acid (CPBA) in the presence of iron(II) polychlorophthalocyanine (Cl16PcFe), iron(II) phthalocyanine (PcFe) and cobalt(II) phthalocyanine (PcCo), results in the formation of the following products: cyclohexene oxide, 2-cyclohexene-1-ol and 2-cyclohexene-1-one. Adipic acid was also formed after long reaction times. The selectivity for 2-cyclohexene-1-one is favoured when Cl16PcFe or PcCo catalysts are employed, while PcFe is selective towards the formation of 2-cyclohexene-1-ol. The Cl16PcFe catalyst is transformed into a μ-oxo dimer (Cl16PcFeIIIOIIIFePcCl16) during the oxidation process. The catalytic process using the unsubstituted PcCoII and PcFeII catalysts involved PcMIII species as an intermediate. The active form of the Cl16PcFe catalyst was stable to degradation in that it was still active even after 4 weeks of continued catalysis.
- Full Text:
- Date Issued: 2004
Determination of 2′, 3′-Dideoxyinosine Using Iron (II) Phthalocyanine Modified Carbon Paste Electrode
- Ozoemena, Kenneth I, Stefan, Raluca-Ioana, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Stefan, Raluca-Ioana , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300298 , vital:57914 , xlink:href="https://doi.org/10.1081/AL-200031940"
- Description: An amperometric sensor, based on carbon paste impregnated with iron (II) phthalocyanine complex (FePc), has been constructed for the assay of anti‐HIV agent dideoxyinosine (didanosine, DDI). Using chronoamperometry (E = +1.04 V versus Ag/AgCl) technique, the amperometric sensor can be used reliably for dideoxyinosine assay at pH 7.4 phosphate buffer in the 1.5–9.5 nmol/L concentration range with a detection limit of 5.7 × 10−10 mol/L. The surface of the electrode can easily be regenerated by simple polishing, obtaining a fresh surface ready for use in a new assay. The new amperometric sensor proved to be highly reliable for the assay of dideoxyinosine purity in raw material as well as for the uniformity content test of Videx® tablets.
- Full Text:
- Date Issued: 2004
- Authors: Ozoemena, Kenneth I , Stefan, Raluca-Ioana , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300298 , vital:57914 , xlink:href="https://doi.org/10.1081/AL-200031940"
- Description: An amperometric sensor, based on carbon paste impregnated with iron (II) phthalocyanine complex (FePc), has been constructed for the assay of anti‐HIV agent dideoxyinosine (didanosine, DDI). Using chronoamperometry (E = +1.04 V versus Ag/AgCl) technique, the amperometric sensor can be used reliably for dideoxyinosine assay at pH 7.4 phosphate buffer in the 1.5–9.5 nmol/L concentration range with a detection limit of 5.7 × 10−10 mol/L. The surface of the electrode can easily be regenerated by simple polishing, obtaining a fresh surface ready for use in a new assay. The new amperometric sensor proved to be highly reliable for the assay of dideoxyinosine purity in raw material as well as for the uniformity content test of Videx® tablets.
- Full Text:
- Date Issued: 2004
Electrochemical and catalytic properties of chromium tetraaminophthalocyanine
- Obirai, Joe, Nyokong, Tebello
- Authors: Obirai, Joe , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300310 , vital:57915 , xlink:href="https://doi.org/10.1016/j.jelechem.2004.06.026"
- Description: Chromium tetraaminophthalocyanine (CrIIITAPc) has been synthesized and its electrochemical and spectroelectrochemical properties reported. The first reduction and oxidation in this complex occur at the central metal, giving CrIITAPc and CrIVTAPc complexes, respectively, the latter having been observed for the first time. The CrIIITAPc species was polymerized onto glassy carbon (GCE) or indium tin oxide (ITO) electrodes and the polymer evolution confirmed by UV/Visible spectroscopy and by scanning electron microscopy. The polymers were employed for the catalytic oxidation of nitrite or nitric oxide, and the catalysis involved the CrIVTAPc−1 species.
- Full Text:
- Date Issued: 2004
- Authors: Obirai, Joe , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300310 , vital:57915 , xlink:href="https://doi.org/10.1016/j.jelechem.2004.06.026"
- Description: Chromium tetraaminophthalocyanine (CrIIITAPc) has been synthesized and its electrochemical and spectroelectrochemical properties reported. The first reduction and oxidation in this complex occur at the central metal, giving CrIITAPc and CrIVTAPc complexes, respectively, the latter having been observed for the first time. The CrIIITAPc species was polymerized onto glassy carbon (GCE) or indium tin oxide (ITO) electrodes and the polymer evolution confirmed by UV/Visible spectroscopy and by scanning electron microscopy. The polymers were employed for the catalytic oxidation of nitrite or nitric oxide, and the catalysis involved the CrIVTAPc−1 species.
- Full Text:
- Date Issued: 2004
Electrochemical studies of manganese tetraamminophthalocyanine monomer and polymer
- Obirai, Joseph, Nyokong, Tebello
- Authors: Obirai, Joseph , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290330 , vital:56738 , xlink:href="https://doi.org/10.1016/j.electacta.2003.11.006"
- Description: Manganese tetraaminophthalocyanine (MnTAPc) has been synthesised. The cyclic voltammetry and spectroelectrochemistry of the complex have been examined. Spectroelectrochemistry has been used to confirm that the species synthesised in this work contains MnIII, giving (OH)MnIIITAPc. The oxidation and reduction couples obtained from cyclic voltammetry have been assigned to MnIVPc−/MnIVPc2− (couple I), MnIVPc2−/MnIIIPc2− (couple I′), MnIIIPc2−/MnIIPc2− (couple II) and MnIIPc2−/MnIIPc3− (couple III). Electropolymerization of the MnTAPc onto either the indium tin oxide or glassy carbon electrode results in the in the formation of a poly-MnTAPc. The poly-MnTAPc shows improved reversibility at low pH. The poly-MnTAPc electrode was employed to analyse glycine.
- Full Text:
- Date Issued: 2004
- Authors: Obirai, Joseph , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290330 , vital:56738 , xlink:href="https://doi.org/10.1016/j.electacta.2003.11.006"
- Description: Manganese tetraaminophthalocyanine (MnTAPc) has been synthesised. The cyclic voltammetry and spectroelectrochemistry of the complex have been examined. Spectroelectrochemistry has been used to confirm that the species synthesised in this work contains MnIII, giving (OH)MnIIITAPc. The oxidation and reduction couples obtained from cyclic voltammetry have been assigned to MnIVPc−/MnIVPc2− (couple I), MnIVPc2−/MnIIIPc2− (couple I′), MnIIIPc2−/MnIIPc2− (couple II) and MnIIPc2−/MnIIPc3− (couple III). Electropolymerization of the MnTAPc onto either the indium tin oxide or glassy carbon electrode results in the in the formation of a poly-MnTAPc. The poly-MnTAPc shows improved reversibility at low pH. The poly-MnTAPc electrode was employed to analyse glycine.
- Full Text:
- Date Issued: 2004