Niobium (Nb) and tantalum (Ta) are found in the same group (VB) of the periodic table of elements and therefore have similar chemical properties, which is the reason why they are difficult to separate. They are usually found together in various minerals of which the most important are columbite ((Fe, Mn, Mg)(Nb, Ta)2O6) and tantalite ((Fe, Mn)(Nb, Ta)2O6). Several methods have been used to separate Nb and Ta. Most methods use very high concentrations of hydrofluoric acid (HF) and sulphuric acid (H2SO4) as the aqueous phase, tributyl phosphate (TBP) as the extractant and methyl isobutyl ketone (MIBK) as the organic phase. High extraction can be achieved, but the reagents used are hazardous. With the increasing demand of both pure Ta and Nb, as well as stricter environmental requirements, a need exists to develop a more efficient and safer technique to separate Ta and Nb. In this project the focus was on the solvent extraction (SX) of Ta and Nb with the possible application in a membrane-based solvent extraction (MBSX) process. For this purpose, eight different extractants were investigated, namely the cation exchangers di-iso-octyl-phosphinic acid (PA) and di-(2-ethylhexyl)-phosphoric acid (D2EHPA), the neutral solvating extractant 2-thenoyl-trifluoro- acetone (TTA), and the anion exchangers Alamine 336, Aliquat 336, 1-octanol, 2-octanol and 3-octanol. The extractant to metal ratio was varied from 0.1:1 to 10:1, while cyclohexane was used as diluent and 3% v/v 1-octanol was used as modifier for the organic phase. In addition, four different acids, hydrochloric acid (HCl), nitric acid (HNO3), sulphuric (H2SO4) and perchloric acid (HClO4), were used at different concentrations to determine the best combination for extraction. First, fluoride salts of Ta and Nb (Ta(Nb)F5) were tested and the optimum results showed that the highest extraction was obtained with PA and D2EHPA, irrespective of the type of acid used. Similarly, irrespective of the acid used, extraction with PA and D2EHPA increased with increasing acid concentration, followed by Alamine 336, Aliquat 336 and then TTA and the octanols. Extraction values of 97% Ta at 15 mol/dm3 and 85% Nb between 12 and 15 mol/dm3 were obtained. Although extraction of both Ta and Nb was achieved with all the acids tested, only H2SO4 showed sufficient separation (log D = 3) of the two metals in the 0 to 2 mol/dm3 acid range and 15 mol/dm3 for PA and D2EHPA, respectively. Precipitation, probably due to hydrolysis of the metals, occurred in the absence of acid when using Alamine 336, Aliquat 336 and TTA. The octanols showed the least amount of extraction of Ta and Nb, irrespective of the acid investigated. The optimum extraction was achieved with an E/M ratio of 3:1 of PA and D2EHPA as the extractant and 10 mol/dm3 H2SO4 in the aqueous phase. The NH4Ta(Nb)F6 salt solution was investigated using the optimum conditions for maximum extraction obtained from the Ta(Nb)F5 experiments, i.e. 4 mol/dm3 H2SO4 with an E/M ratio above 3:1 for the extractant PA and 4 mol/dm3 H2SO4 with an E/M ratio of 20:1 for the extractant D2EHPA. Kinetic equilibrium for PA was reached after 10 minutes and for D2EHPA after 20 minutes. The highest extraction of Ta (100%) above 3 mol/dm3 H2SO4 and Nb (54%) at 8 mol/dm3 with the highest separation factor of 4.7 with PA was achieved, followed by the 100% extraction of Ta above 5 mol/dm3 and 40% Nb at 10 mol/dm3 with the highest separation factor of 4.9 in D2EHPA. Although the aim of this study was the extraction and separation of Ta and Nb, the recovery or back extraction of the metals from the organic phase, as well as the membrane-based solvent extraction (MBSX) was briefly investigated. From the preliminary results obtained it became apparent that further research into the different aspects, including the type of stripping agent used, stripping agent concentration, effect of Ta to Nb ratio and different sources of Ta and Nb is needed to obtain the optimum conditions for the MBSX process and the subsequent recovery of Ta and Nb. / Thesis (MSc (Chemistry))--North-West University, Potchefstroom Campus, 2013.

Niobium (Nb) and tantalum (Ta) are found in the same group (VB) of the periodic table of elements and therefore have similar chemical properties, which is the reason why they are difficult to separate. They are usually found together in various minerals of which the most important are columbite ((Fe, Mn, Mg)(Nb, Ta)2O6) and tantalite ((Fe, Mn)(Nb, Ta)2O6). Several methods have been used to separate Nb and Ta. Most methods use very high concentrations of hydrofluoric acid (HF) and sulphuric acid (H2SO4) as the aqueous phase, tributyl phosphate (TBP) as the extractant and methyl isobutyl ketone (MIBK) as the organic phase. High extraction can be achieved, but the reagents used are hazardous. With the increasing demand of both pure Ta and Nb, as well as stricter environmental requirements, a need exists to develop a more efficient and safer technique to separate Ta and Nb. In this project the focus was on the solvent extraction (SX) of Ta and Nb with the possible application in a membrane-based solvent extraction (MBSX) process. For this purpose, eight different extractants were investigated, namely the cation exchangers di-iso-octyl-phosphinic acid (PA) and di-(2-ethylhexyl)-phosphoric acid (D2EHPA), the neutral solvating extractant 2-thenoyl-trifluoro- acetone (TTA), and the anion exchangers Alamine 336, Aliquat 336, 1-octanol, 2-octanol and 3-octanol. The extractant to metal ratio was varied from 0.1:1 to 10:1, while cyclohexane was used as diluent and 3% v/v 1-octanol was used as modifier for the organic phase. In addition, four different acids, hydrochloric acid (HCl), nitric acid (HNO3), sulphuric (H2SO4) and perchloric acid (HClO4), were used at different concentrations to determine the best combination for extraction. First, fluoride salts of Ta and Nb (Ta(Nb)F5) were tested and the optimum results showed that the highest extraction was obtained with PA and D2EHPA, irrespective of the type of acid used. Similarly, irrespective of the acid used, extraction with PA and D2EHPA increased with increasing acid concentration, followed by Alamine 336, Aliquat 336 and then TTA and the octanols. Extraction values of 97% Ta at 15 mol/dm3 and 85% Nb between 12 and 15 mol/dm3 were obtained. Although extraction of both Ta and Nb was achieved with all the acids tested, only H2SO4 showed sufficient separation (log D = 3) of the two metals in the 0 to 2 mol/dm3 acid range and 15 mol/dm3 for PA and D2EHPA, respectively. Precipitation, probably due to hydrolysis of the metals, occurred in the absence of acid when using Alamine 336, Aliquat 336 and TTA. The octanols showed the least amount of extraction of Ta and Nb, irrespective of the acid investigated. The optimum extraction was achieved with an E/M ratio of 3:1 of PA and D2EHPA as the extractant and 10 mol/dm3 H2SO4 in the aqueous phase. The NH4Ta(Nb)F6 salt solution was investigated using the optimum conditions for maximum extraction obtained from the Ta(Nb)F5 experiments, i.e. 4 mol/dm3 H2SO4 with an E/M ratio above 3:1 for the extractant PA and 4 mol/dm3 H2SO4 with an E/M ratio of 20:1 for the extractant D2EHPA. Kinetic equilibrium for PA was reached after 10 minutes and for D2EHPA after 20 minutes. The highest extraction of Ta (100%) above 3 mol/dm3 H2SO4 and Nb (54%) at 8 mol/dm3 with the highest separation factor of 4.7 with PA was achieved, followed by the 100% extraction of Ta above 5 mol/dm3 and 40% Nb at 10 mol/dm3 with the highest separation factor of 4.9 in D2EHPA. Although the aim of this study was the extraction and separation of Ta and Nb, the recovery or back extraction of the metals from the organic phase, as well as the membrane-based solvent extraction (MBSX) was briefly investigated. From the preliminary results obtained it became apparent that further research into the different aspects, including the type of stripping agent used, stripping agent concentration, effect of Ta to Nb ratio and different sources of Ta and Nb is needed to obtain the optimum conditions for the MBSX process and the subsequent recovery of Ta and Nb. / Thesis (MSc (Chemistry))--North-West University, Potchefstroom Campus, 2013.

Gold mine tailings material facilities are characterized by sparse vegetation and an abundance of dust. Mine tailings facilities are examples of extreme geotechnical and geochemical conditions which make it almost impossible for higher plants to establish and grow without rehabilitation intervention. In most cases higher plants such as grasses and trees are the focus areas for rehabilitation, but, having a look at something a little smaller such as biological crusts, it is seen that these micro-organisms play very important roles in any ecosystem. Various studies have shown that biological crusts, consisting of micro-organisms such as lichens, algae and cyanoprokaryotes enhance the soil quality by binding soil particles together, forming aggregates which counteract the erosive forces of wind and water. They play a part in nitrogen and carbon fixation, increase the soil surface temperature and increase the water retention of the soil. Thus, these organisms improve the overall health of the soil, which will in time encourage the successful establishment of higher plants. The aim of this study was to investigate the presence of cyanoprokaryotes and soil algae on mine tailings storage facilities that have been rehabilitated for different periods of time as well as to correlate the presence of these species with the physical and chemical characteristics of the mine tailings material. Chemical, physical and biological analyses of soil samples were done. Some of the ecologically important and dominant species were isolated and protocols were developed in order to identify the most successful manner in which to re-inoculate the organisms to a chosen substrate and how to measure biomass. Due to the immense cost of standard rehabilitation practices there is a need for a more cost effective, sustainable manner in which to protect the tailings material against the erosive forces of wind and water with as little input as possible. The influence of an organism cultured in normal Bold’s Basal medium (BBM) growth medium, BBM growth medium with half the phosphate concentration and BBM growth medium with half the nitrate concentration on the establishment of a biological soil crust (BSC) was tested. To test the influence of the inoculums already present in the tailings material and in the air, trials with mulch, water and nutrients without the addition of an organism was also investigated. This was done in the controlled environment of a glasshouse, as well as in field conditions. The biomass of the cyanoprokaryotes and algae, as well as the soil surface strength was also tested. The results show that the time of rehabilitation did not have an influence on the cyanoprokaryotes as well as algal species that occurred on the tailings material. Chlorella sp., Chlorococcum sp. and Klebsormidium sp. were present on all six sites, except on the fresh material and 15 year old material where no rehabilitation has been done. As for dominance; Chlamydomonas sp., Chlorococcum sp., Klebsormidium sp. and Phormidium sp. were dominant on all six sites except for the fresh material, where nothing grew. An array of methods exists for measuring algal biomass as a measure of growth. During the development of protocols for further use in investigating the growth of algae, the extraction solvent ethanol, for use in chlorophyll a extraction, was identified as the most sufficient. The re-inoculation of cyanoprokaryotes and soil algae onto a chosen substrate is most successful when pouring the organisms, cultured in growth medium and 0.1% agar, over the substrate. During the glasshouse trials the influence of the growth medium and growth medium with half the nitrate and half the phosphate concentrations showed that Chlamydomonas sp. produced the highest biomass when cultured in BBM. With Nostoc sp. the highest biomass occurred with culturing in BBM and BBM with half the phosphate concentration. Microcoleus vaginatus showed no significant difference when cultured in the three different growth mediums (BBM, BBM with half the nitrate concentration and BBM with half the phosphate concentration). Overall Nostoc sp. produced the highest biomass (34.33 μg/g), followed by Microcoleus vaginatus (17.05 μg/g) and Chlamydomonas sp. (6.12 μg/g). Soil surface strength, measured with a hand held penetrometer showed that Chlamydomonas sp. cultured in BBM growth medium produced the most stable crust (2.58 kg/cm2), although it had the lowest biomass measurements (6.12 μg/g). Nostoc sp. produced the highest biomass (34.44 μg/g), but had the lowest soil surface strength results (1.75 kg/cm2). Microcoleus vaginatus proved to be the species with high biomass production (17.05 μg/g), as well as high soil surface strength (2.08 kg/cm2). M. vaginatus is also a pioneer species and is therefore a good choice as primary inoculum on bare tailings material. It was decided to use Nostoc sp. in the field trials due to its high biomass and Microcoleus vaginatus due to the high soil surface strength produced. Despite the occurrence of a severe thunder storm on the afternoon of application and poor water management during the field trials the significance of water on the establishment of soil algae and cyanoprokaryotes on tailings material was determined. / MSc (Environmental Sciences), North-West University, Potchefstroom Campus, 2014

Gold mine tailings material facilities are characterized by sparse vegetation and an abundance of dust. Mine tailings facilities are examples of extreme geotechnical and geochemical conditions which make it almost impossible for higher plants to establish and grow without rehabilitation intervention. In most cases higher plants such as grasses and trees are the focus areas for rehabilitation, but, having a look at something a little smaller such as biological crusts, it is seen that these micro-organisms play very important roles in any ecosystem. Various studies have shown that biological crusts, consisting of micro-organisms such as lichens, algae and cyanoprokaryotes enhance the soil quality by binding soil particles together, forming aggregates which counteract the erosive forces of wind and water. They play a part in nitrogen and carbon fixation, increase the soil surface temperature and increase the water retention of the soil. Thus, these organisms improve the overall health of the soil, which will in time encourage the successful establishment of higher plants. The aim of this study was to investigate the presence of cyanoprokaryotes and soil algae on mine tailings storage facilities that have been rehabilitated for different periods of time as well as to correlate the presence of these species with the physical and chemical characteristics of the mine tailings material. Chemical, physical and biological analyses of soil samples were done. Some of the ecologically important and dominant species were isolated and protocols were developed in order to identify the most successful manner in which to re-inoculate the organisms to a chosen substrate and how to measure biomass. Due to the immense cost of standard rehabilitation practices there is a need for a more cost effective, sustainable manner in which to protect the tailings material against the erosive forces of wind and water with as little input as possible. The influence of an organism cultured in normal Bold’s Basal medium (BBM) growth medium, BBM growth medium with half the phosphate concentration and BBM growth medium with half the nitrate concentration on the establishment of a biological soil crust (BSC) was tested. To test the influence of the inoculums already present in the tailings material and in the air, trials with mulch, water and nutrients without the addition of an organism was also investigated. This was done in the controlled environment of a glasshouse, as well as in field conditions. The biomass of the cyanoprokaryotes and algae, as well as the soil surface strength was also tested. The results show that the time of rehabilitation did not have an influence on the cyanoprokaryotes as well as algal species that occurred on the tailings material. Chlorella sp., Chlorococcum sp. and Klebsormidium sp. were present on all six sites, except on the fresh material and 15 year old material where no rehabilitation has been done. As for dominance; Chlamydomonas sp., Chlorococcum sp., Klebsormidium sp. and Phormidium sp. were dominant on all six sites except for the fresh material, where nothing grew. An array of methods exists for measuring algal biomass as a measure of growth. During the development of protocols for further use in investigating the growth of algae, the extraction solvent ethanol, for use in chlorophyll a extraction, was identified as the most sufficient. The re-inoculation of cyanoprokaryotes and soil algae onto a chosen substrate is most successful when pouring the organisms, cultured in growth medium and 0.1% agar, over the substrate. During the glasshouse trials the influence of the growth medium and growth medium with half the nitrate and half the phosphate concentrations showed that Chlamydomonas sp. produced the highest biomass when cultured in BBM. With Nostoc sp. the highest biomass occurred with culturing in BBM and BBM with half the phosphate concentration. Microcoleus vaginatus showed no significant difference when cultured in the three different growth mediums (BBM, BBM with half the nitrate concentration and BBM with half the phosphate concentration). Overall Nostoc sp. produced the highest biomass (34.33 μg/g), followed by Microcoleus vaginatus (17.05 μg/g) and Chlamydomonas sp. (6.12 μg/g). Soil surface strength, measured with a hand held penetrometer showed that Chlamydomonas sp. cultured in BBM growth medium produced the most stable crust (2.58 kg/cm2), although it had the lowest biomass measurements (6.12 μg/g). Nostoc sp. produced the highest biomass (34.44 μg/g), but had the lowest soil surface strength results (1.75 kg/cm2). Microcoleus vaginatus proved to be the species with high biomass production (17.05 μg/g), as well as high soil surface strength (2.08 kg/cm2). M. vaginatus is also a pioneer species and is therefore a good choice as primary inoculum on bare tailings material. It was decided to use Nostoc sp. in the field trials due to its high biomass and Microcoleus vaginatus due to the high soil surface strength produced. Despite the occurrence of a severe thunder storm on the afternoon of application and poor water management during the field trials the significance of water on the establishment of soil algae and cyanoprokaryotes on tailings material was determined. / MSc (Environmental Sciences), North-West University, Potchefstroom Campus, 2014

The ochratoxins, metabolites of certain Aspergillus and Penicillium species are the first group of mycotoxins discovered subsequent to the epoch-making discovery of the aflatoxins. Ochratoxin A (OTA) is a very important mycotoxin owing to its frequent occurrence in nature, its established role in Danish porcine nephropathy and in poultry mycotoxicoses and its implicated role in Balkan endemic nephropathy and urinary system tumors among population groups in North Africa. Chapters 2 and 3 highlight the importance of OTA and the research currently being done on mycotoxins. These efforts are focused on the molecular genetics of toxinogenic fungi; the mechanism of their action; species differences in metabolism and pharmacokinetics; quantification of mycotoxins; risk assessments on the exposure of man and animals to mycotoxins and regulations for the control of mycotoxin contamination. Methods developed to analyse OTA in different matrices by using reversed phase high performance-liquid chromatography with fluorescence detection and tandem liquid chromatography-mass spectrometry techniques are described in Chapter 10. Amino propyl solid phase extraction columns were used for the first time in cleanup steps of ochratoxin analysis. These techniques and methods were applied to the first survey on the levels of OTA in coffee on the South African retail market (Chapter 5). The results suggest that the levels of OT A in the coffee on the South African market are somewhat higher than the levels of OTA in coffees on the European market. The possibility to biologically produce different halogen-ochratoxins by supplementing the growth medium of Aspergillus ochraceus with halogen salts was investigated. Bromoochratoxin A was produced for the first time in this way. Supplementation of inoculated wheat with potassium iodide and -fluoride resulted in the poisoning of the yeast and no iodoor fluoro-ochratoxin B was produced. It was found that Aspergillus ochraceus produced OTA in higher yields at elevated levels of potassium chloride. This finding has important commercial applications in the production ofOTA (Chapter 4). The ochratoxins are hydrolyzed in vivo by carboxypeptidase A. The hydrolysis of the ochratoxins and analogues by carboxypeptidase A was measured in vitro in a structurefunction relation study by employing mass spectrometric techniques. The kinetic data of the ochratoxins were compared to the values of a number of synthesized structural analogues. It was found that the halogen containing analogues had lower turnovers than their des-halo analogues. There were no substantial differences in the kinetic data between the different halogen containing analogues (Chapter 8). The toxicokinetics of OTA in vervet monkeys were determined for the first time. The clearance of OTA from the plasma suggested a two-compartment model and the elimination half-life was determined to be 19-21 days. The half-life of OTA in humans was determined by allometric calculations to be 46 days. We came to the conclusion that the long term consumption of OT A contaminated foods will lead to potentially hazardous levels of the toxin in the body (Chapter 9). This hypothesis can be substantiated by the incidence of OTA in the blood of various population groups. Possible ways to decontaminate OT A contaminated foods by degrading the compound biologically with yeast; moulds or lipases to non-toxic compounds were investigated. Eight moulds, 323 yeasts and 23 lipases were screened for ochratoxin degradation. A lipase from Aspergillus niger is the first lipase that was proven to degrade OTA (Chapter 7). Four yeasts were found to degrade OT A of which one, Trichosporon mucoides degraded OTA substantially within 48 hours in a growing culture (Chapter 6). In addition to this first report of yeasts which have the ability to degrade OTA, the fungi Cochliobolus sativus, Penicillium islandicum and Metarhizium anispoliae also proved to degrade OT A. OT A was degraded in all instances to the non-toxic ochratoxin a and the amino acid phenylalanine. / Thesis (PhD (Chemistry))--Potchefstroom University for Christian Higher Education, 2000

The ochratoxins, metabolites of certain Aspergillus and Penicillium species are the first group of mycotoxins discovered subsequent to the epoch-making discovery of the aflatoxins. Ochratoxin A (OTA) is a very important mycotoxin owing to its frequent occurrence in nature, its established role in Danish porcine nephropathy and in poultry mycotoxicoses and its implicated role in Balkan endemic nephropathy and urinary system tumors among population groups in North Africa. Chapters 2 and 3 highlight the importance of OTA and the research currently being done on mycotoxins. These efforts are focused on the molecular genetics of toxinogenic fungi; the mechanism of their action; species differences in metabolism and pharmacokinetics; quantification of mycotoxins; risk assessments on the exposure of man and animals to mycotoxins and regulations for the control of mycotoxin contamination. Methods developed to analyse OTA in different matrices by using reversed phase high performance-liquid chromatography with fluorescence detection and tandem liquid chromatography-mass spectrometry techniques are described in Chapter 10. Amino propyl solid phase extraction columns were used for the first time in cleanup steps of ochratoxin analysis. These techniques and methods were applied to the first survey on the levels of OTA in coffee on the South African retail market (Chapter 5). The results suggest that the levels of OT A in the coffee on the South African market are somewhat higher than the levels of OTA in coffees on the European market. The possibility to biologically produce different halogen-ochratoxins by supplementing the growth medium of Aspergillus ochraceus with halogen salts was investigated. Bromoochratoxin A was produced for the first time in this way. Supplementation of inoculated wheat with potassium iodide and -fluoride resulted in the poisoning of the yeast and no iodoor fluoro-ochratoxin B was produced. It was found that Aspergillus ochraceus produced OTA in higher yields at elevated levels of potassium chloride. This finding has important commercial applications in the production ofOTA (Chapter 4). The ochratoxins are hydrolyzed in vivo by carboxypeptidase A. The hydrolysis of the ochratoxins and analogues by carboxypeptidase A was measured in vitro in a structurefunction relation study by employing mass spectrometric techniques. The kinetic data of the ochratoxins were compared to the values of a number of synthesized structural analogues. It was found that the halogen containing analogues had lower turnovers than their des-halo analogues. There were no substantial differences in the kinetic data between the different halogen containing analogues (Chapter 8). The toxicokinetics of OTA in vervet monkeys were determined for the first time. The clearance of OTA from the plasma suggested a two-compartment model and the elimination half-life was determined to be 19-21 days. The half-life of OTA in humans was determined by allometric calculations to be 46 days. We came to the conclusion that the long term consumption of OT A contaminated foods will lead to potentially hazardous levels of the toxin in the body (Chapter 9). This hypothesis can be substantiated by the incidence of OTA in the blood of various population groups. Possible ways to decontaminate OT A contaminated foods by degrading the compound biologically with yeast; moulds or lipases to non-toxic compounds were investigated. Eight moulds, 323 yeasts and 23 lipases were screened for ochratoxin degradation. A lipase from Aspergillus niger is the first lipase that was proven to degrade OTA (Chapter 7). Four yeasts were found to degrade OT A of which one, Trichosporon mucoides degraded OTA substantially within 48 hours in a growing culture (Chapter 6). In addition to this first report of yeasts which have the ability to degrade OTA, the fungi Cochliobolus sativus, Penicillium islandicum and Metarhizium anispoliae also proved to degrade OT A. OT A was degraded in all instances to the non-toxic ochratoxin a and the amino acid phenylalanine. / Thesis (PhD (Chemistry))--Potchefstroom University for Christian Higher Education, 2000