3. Electronic Theses and Dissertations (ETDs) - All submissions
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Item Silica and maghemite nanoparticles for the remediation of acid mine drainage-contaminated waters and Nanoparticle modification of metal uptake by a freshwater alga-Scenedesmus sp(2015-01-30) Etale, AnitaAims: The adsorptive removal of Cu, Mn, Hg and U by silica and maghemite nanoparticles (NPs) under acid mine drainage (AMD) conditions was investigated with the aim of assessing the applicability of NPs for remediation of AMD-contaminated water. The effect of NPs on metal uptake by algae, an increasingly popular remediation alternative, was also investigated. Methods: NP and algal metal removal were quantified by batch experiments using commercially prepared, bare and amine-functionalised silica-carbon hybrid NPs characterised for size, surface area, porosity, crystallinity, elemental composition and hydrodynamic size. Metal uptake by algae was quantified in the presence and absence of NPs. Results: Silica and maghemite NPs can be used for the adsorptive removal of Cu, Mn, Hg and U from AMD-contaminated surface and ground water. NP metal uptake was rapid and equilibria were attained within 5 minutes with silica and maghemite NPs, and within 45 minutes with amine-functionalised hybrid NPs. Adsorption efficiencies for Cu, Mn, Hg and U at pH 3 were 52, 56, 56 and 49%, respectively with silica and 56, 52, 75 and 50%, respectively, with maghemite NPs. Metal removal was enhanced by >10% in solutions containing ferric, manganese or sulphate ions, although Cu removal was inhibited in solutions with a >1 Mn:Cu ratio. Despite the presence of high affinity amine groups in hybrid NPs, Cu removal was only 52% due to the low surface area of the adsorbent. The comparative study with Hg, however, showed that surface area was not the only determinant of adsorption efficiency: maghemite NPs with a specific surface area ~15 times less than silica adsorbed 21% more Hg. Metal removal by Scenedesmus sp. was enhanced by 12-27% in solutions containing NPs due to the greater sorption surface areas. NPs also modified metal partitioning in algal cells: intracellular concentrations were lower and extracellular concentrations higher in solutions containing NPs relative to controls (no NPs). Conclusion: Silica and maghemite NPs can be applied for the adsorptive removal of Cu, Mn, Hg and U from AMD-contaminated water and to improve the efficiency of phycoremediation by Scenedesmus sp. These findings also point to the possibility of retardation of metals by NPs during their transportation from tailings and contaminated sites. Their partitioning to NPs and the strength of the interactions thereof can determine the prevalence of the metals in solution or in the solid phase.Item An investigation of mineralisation controls in the upper section of the Platreef in the southern sector, on Turfspruit, Northern Limb, Bushveld Complex, South Africa(2014-06-12) Kekana, Sello MelvynGeochemical, mineralogical and tenor variation studies were carried out on the cores from UMT040, UMT064 and UMT063, located in the Flatreef on Turfspruit, in the southern sector of the Platreef. The investigation comprised three objectives (1) to identify controls on mineralisation in the upper section of the Platreef, (2) to construct a 3D PGE tenor model, and (3) to test whether the new geological interpretation on Turfspruit correlates with the eastern and western limbs of the Bushveld Complex. The above-mentioned holes were used for geochemical analyses of major and trace elements; and UMT064 was also used for orthopyroxene microprobe analyses. For construction of the tenor model, a total of 276 drill holes were used. The distance between drill holes for geochemical studies is 145 m and 175 m respectively; and for the tenor model is approximately 100 m. The outcomes of the study have demonstrated that the upper section of the Platreef comprise at least four lithological units i.e. the topmost portion of T1, lowermost portion of T1, T2 Upper and T2 Lower that can be interpreted to have been formed by four separate pulses of magma. Considering the possibility of the T2 Lower being metamorphosed calc-silicates, this reduces the number of magma pulses to three. This is supported by the mineralogy, geochemical content and tenor variations. The T1 is made up of an orthopyroxenite (feldspathic in places), the T2 Upper comprised a pegmatoidal orthopyroxenite (also feldspathic in places) and the T2 Lower is made up of a harzburgite. High grade PGE, Ni and Cu mineralisation was found to occur within two zones in the upper section of the Platreef i.e. the T1m and T2 (Upper and Lower). Mineralisation occurs in the form of base metal sulphides such as pyrrhotite, pentlandite and chalcopyrite; and PGEs are dominated by amphoterics (PGE-arsenides, tellurides, antimonides and bismuthinides). These amphoterics are associated with base metal sulphides. The sulphides in both the T1m and T2 are interstitial. PGE minerals such as michenerite, sperrylite, hollingworthite and cooperite are present in the study area. In the T2, an increase in sulphide content and PGE grades are generally associated with the presence of the “main” chromitite stringer/ seam at the contact between a feldspathic pyroxenite (T1) and the coarse-grained to pegmatoidal pyroxenite (T2 Upper). Several other chromitites might be present above and below this contact, and it has been noted that not all of those chromitites are associated with an increase in sulphide content and higher PGE grades. PGE grades were found to be higher in T2 Upper than in T2 Lower, whereas, the base metals (particularly Ni) are generally higher in T2 Lower. In the T1m, mineralisation occurs close to the contact between the feldspathic pyroxenite and orthopyroxenite, but only the orthopyroxenite hosts the sulphides. Chromitite stringers rarely occur in the T1m. Where present, they generally occur at the top of the mineralised zone. The sulphides in both the T1m and T2 are thought to have resulted from separate and different processes. Those in the T1m are thought to have resulted from a fractional segregation process, whereas the sulphides in the T2 were thought to have been emplaced in bulk or as a mush. The 3D PGE tenor model has demonstrated that the tenor in both the T1 and T2 are higher than previously thought for the northern limb of the Bushveld Complex. Tenors in the T1 reach up to 700 ppm, whereas tenors of about 1000 ppm were recorded in the T2. These tenors are comparable to the tenors measured from the sulphide melt inclusions elsewhere in the northern limb. Tenors are the highest in the northwestern part of Turfspruit and they gradually decrease towards the southeast. Both the T1 and T2 are dominated by a tenor of about 100 ppm. In the T1, a tenor of 250 ppm is dominant in the northwestern and southeastern parts of the study area, whereas in the T2 it is only dominant in the northwestern part. Vertical variation in tenors has shown that the tenors are the highest in the topmost portion of the T1 and at the top of T2 Upper (below the T1-T2 contact). The T1 has been found to be comparable with the Merensky Reef due to the following: (a) similarities with respect to major and trace element compositions of whole rock analyses; (b) Cr/MgO ratios which are greater than 80; and (c) similarities in the pyroxene content excluding the MgO/((MgO)+FeO) ratio and CaO contents; and in the PGE tenor of the sulphides. In addition, the T1 has many of the characteristics of the model proposed by Naldrett et al (2009) for the formation of the Merensky Reef in the western Bushveld. However, the differences between the T1 and the Merensky Reef were also noted i.e. the MgO/((MgO)+FeO) ratios in this study are lower (averaging 0.71) than the Mg# reported for the Merensky Reef (Mg#78-83), the upper Critical Zone (Mg#78-84) and elsewhere in the Platreef north of Turfspruit. The CaO levels (representing the wollastonite component of the orthopyroxene) at Turfspruit are higher (>2 wt %) compared to the Merensky Cyclic Unit and other parts of the northern limb where the CaO levels are below 2 wt %. This is an indication that the pyroxene composition at Turfspruit is more evolved compared to the Merensky Reef.Item Geophysical studies of the crust and uppermost mantle of South Africa.(2014-03-05) Kgaswane, Eldridge MaungweThe general aim of this thesis is to investigate heterogeneity in the structure of the crust and uppermost mantle of Archaean and Proterozoic terrains in southern Africa and to use the findings to advance our understanding of Precambrian crustal genesis. Teleseismic, regional and local seismic recordings by the broadband stations of the Southern African Seismic Experiment (SASE), Kimberley array, South African National Seismograph Network (SANSN) and the Global Seismic Network (GSN) are used in the inversion procedures to address the aim of this thesis. In the first part of the thesis, the nature of the lower crust across the southern African shield is investigated by jointly inverting receiver functions and Rayleigh wave group velocities. The resultant Vs models show that much of southern Africa has a lower crust that is mafic in composition, whereas the western parts of the Kaapvaal and Zimbabwe Cratons have a lower crust that is intermediate-to-felsic in composition probably due to rifting. The second part of the thesis evaluates the “dipping-sheet” and “continuous-sheet” models of the Bushveld Complex using better-resolved seismic models derived in a two-step approach, employing high-frequency Rayleigh wave group velocity tomography and the joint inversion of high-frequency receiver functions and 2–60 sec Rayleigh wave group velocities. The resultant seismic models favor a “continuous-sheet” model of the Bushveld Complex, although detailed modelling near the centre of the Complex shows that the subsurface mafic layering could be disrupted. The third part of the thesis, is focused on jointly inverting high-frequency teleseismic receiver functions and 10–60 sec Rayleigh wave group velocities to place shear wave velocity constraints on the source of the Beattie Magnetic Anomaly (BMA) at depth and to evaluate existing geophysical models of the BMA source. The resultant Vs models across the BMA suggest the BMA source to be at upper to middle crustal depths (5–20 km) with high velocity layers (≥ 3.5 km/s). Further to this, is a lower crust that is highly mafic (Vs ≥ 4.0 km/s) and a crust beneath the BMA that is on average thicker than 40 km. Plausible models of the BMA source are massive sulphide ore bodies and/or mineralized granulite-facies mid-crustal rocks and/or mineralized Proterozoic anorthosites. v Overall, the findings in this research project are consistent with the broad features of a previous model of Precambrian lithospheric evolution but allows for refinements of that model.Item Middle Permian continental biodiversity changes as reflected in the Beaufort Group of South Africa: a bio-and lithostratigraphic review of the Eodicynodon, Tapinocephalus and Pristerognathus assemblage zones(2014-03-04) Day, Michael OliverThe fluvio-lacustrine rocks of the Beaufort Group, South Africa have long been known for their tetrapod fossil record, which is the richest and most complete Middle Permian to Middle Triassic record for any terrestrial sequence in the world. The abundance of fossil material has enabled the Beaufort Group to be biostratigraphically subdivided into between 8 and 10 tetrapod assemblage zones, of which the lowest three (Eodicynodon, Tapinocephalus and Pristerognathus) are attributed to the Middle Permian. These lower assemblage zones record the earliest therapsiddominated faunas and, because they were recorded during a largely uninterrupted period of deposition, make the Beaufort Group the only place in the world where biodiversity change through the terrestrial Middle Permian can be effectively studied. In the last two decades, much interest has focused on an extinction of marine invertebrates at or close to the end of the Middle Permian (Guadalupian epoch), but the existence of a concurrent extinction in the terrestrial realm is contentious. The Beaufort Group is already well known to record the Permo-Triassic Mass Extinction but it also records an earlier extinction at the top of the Tapinocephalus Assemblage Zone (AZ). This extinction is very poorly understood but recent radiometric dates for many Permian assemblage zones of the Beaufort Group have confirmed a Middle Permian age for Eodicynodon, Tapinocephalus and Pristerognathus assemblage zones and suggest that the end-Tapinocephalus AZ extinction may coincide with the marine extinctions. A recently produced GIS database that accommodates all Beaufort Group fossil material curated in South Africa formed the basis on which the stratigraphic range of individual specimens was calculated. To put the fossil localities in a stratigraphic context, lithostratigraphic information was retrieved from the literature and extensive fieldwork was conducted, which measured stratigraphic sections in key areas and traced the surface outcrop of lithostratigraphic units. In order to compensate for lateral variations in lithostratigraphy, the basin was split into sectors, each represented by a stratigraphic section. The stratigraphic ranges of fossil specimens and, subsequently, of genera and families could then be calculated and a workable biostratigraphic subdivision of the Middle Permian Beaufort Group proposed. The Abrahamskraal Formation, which forms the majority of the Middle Permian Beaufort sequence, can be divided into six lithostratigraphic members based on the occurrence of sandstone ‘packages’. These members were traced laterally across the Basin and their correspondence with fining-upwards cycles was refined and correlated with the newly defined biostratigraphic units. This refined two-pronged stratigraphic subdivision allowed the recognition of a waning period of subsidence in the proximal sector of the Karoo Basin during the Middle Permian. Stratigraphic ranges of individual genera were found to be far more heterogeneous than previously recognised. Dicynodont genera are useful biostratigraphic indicators due to their relative abundance and well-defined stratigraphic ranges, while dinocephalians and pareiasaurs are clustered in the upper part of the Abrahamskraal Formation. The stratigraphic range of Eodicynodon extends further up in the Abrahamskraal Formation than was previously recognised. The Tapinocephalus AZ is restricted to approximately the upper fifth of the Abrahamskraal Formation and is characterised by advanced tapinocephalid dinocephalians and the pareiasaur Bradysaurus. Between these two biozones is a stratigraphic interval dubbed the mid- Abrahamskraal Formation Transition Zone, where both Eodicynodon and advanced tapinocephalids coexisted. A 75 % loss of generic diversity occurred between the upper Tapinocephalus AZ and the base of the Pristerognathus AZ, which corresponds to a stratigraphic interval between the mid-Karelskraal Member of the Abrahamskraal Formation and the mid- Poortjie Member of the Teekloof Formation. Several taxa that survive the end- Tapinocephalus AZ extinction, and are relatively common in the overlying Pristerognathus AZ (scylacosaurid therocephalians, the dicynodont genus Eosimops and the parareptile Eunotosaurus), all became extinct in the upper Poortjie Member at a time when generic originations are increasing. This suggests a second wave of extinctions in a similar fashion to that recorded at the Permo-Triassic boundary.Item Stratigraphy and sedimentology of the middle Permian Abrahamskraal formation (Tapinocephalus Assemblage Zone) in the southern Karoo around Merweville, South Africa.(2014-02-07) Jirah, SifelaniA study of the Abrahamskraal Formation in the area around Merweville, in the southwestern corner of the Karoo Basin has revealed the presence of traceable lithological units with lateral continuity throughout the study area. The stratigraphic section measured in this part of the basin matches the section measured by Jordaan, (1990) south of Leeu Gamka, with a basal arenaceous unit overlain by a predominantly argillaceous succession. The thickness of the Abrahamskraal Formation in this part of the Karoo Basin in 2565m, charactersized by a braided depositional environment in the lower 2075m and a meandering depositional environment in the upper 490m. Biostratigraphically the succession comprises a basal Eodicynodon Assemblage Zone which constitutes the lower 1104m and this is overlain by a 1461m thick Tapinocephalus Assemblage Zone whose upper limit is 21m below the Poortjie Member of the Teekloof Formation. This study has also corroborated the work by earlier authors who proposed a northeasterly palaeoflow direction as well as contributing to the global correlation of the Middle Permian terrestrial tetrapod faunas where the Eodicynodon Assemblage Zone correlates with the fauna from the Russian Ocher & Ischeevo; fauna of China’s Xidagou Formation and Rio da Rosto fauna of Brazil while the Tapinocephalus Assemblage Zone fauna corrletaes with fauna from Mezen and Ischeevo in Russia, Posto Queimado fauna in Brazil and those from the Madumabisa strata of Zimbabwe.Item Platinum-group mineral assemblages in the Platreef on Tweefontein, Northern Bushveld complex, South Africa(2013-02-04) McCutcheon, ShaunaThe Platreef occurs at the base of the Northern Limb of the Bushveld Complex and is variably mineralised with PGE, Cu, and Ni. The Platreef varies in thickness from a few meters to a few hundred meters and rests on progressively older sediments of the Transvaal Supergroup and Archaean granite basement northwards. Recent studies have highlighted the importance of magmatic processes, contamination of the magma by footwall rocks and syn- and post metasomatic fluid activity on the observed mineralisation. Along the Platreef strike, the PGE grade profiles are generally top-loaded from Overysel to Tweefontein North and more variable and bottom loaded from Tweefontein Hill southwards emphasizing the importance of the change in mineralisation style at Tweefontein in relation to the whole Platreef. This study presents the first significant PGM data on the Tweefontein farm, including ten boreholes along strike, providing insight into the distinctly different PGE mineralisation styles observed. Samples were selected based on assay data, varying rock types, stratigraphic position and proximity to geological features. The selected samples were investigated using petrography, geochemistry and the automated SEM techniques of QEMSCAN and MLA. Over 9000 PGM were analysed forming one of the most comprehensive PGM studies on the Platreef to date. The lowermost footwall intersected along the Tweefontein strike is banded ironstone of the Penge Formation. This is overlain by a metasedimentary footwall package, of variable thickness, derived from the shales and dolomites of the Duitschland Formation. Iron-rich, recrystallised, noritic sills occur at the base of the Platreef and are thought to represent sills which intruded prior to the emplacement of the Platreef. A pre- and possibly syn-Bushveld structural control resulted in irregular floor topography defined by a topographic footwall high in the central Tweefontein area and topographic depressions at Tweefontein North and Tweefontein Hill. The depression areas at Tweefontein are similar to the footwall basins at Turfspruit to the south, in which the Platreef is more lithologically complex compared to the footwall high areas. The footwall basins at Tweefontein and Turfspruit contain basal massive and submassive sulphides, which may not necessarily carry significant PGE grade. The Platreef lithologies at Tweefontein are composed of pyroxenites and norites with minor harzburgitic lithologies and contain numerous cross-cutting granitic veins. Xenoliths/interlayers of metamorphosed Duitschland lithologies occur primarily near the base of the Platreef, but also in the middle and upper Platreef sequence reflecting roof pendants. Unlike the Platreef on the farms adjacent to Tweefontein, the Platreef and footwall lithologies are relatively unaltered, but localised serpentinisation and chloritisation occur within harzburgitic lithologies and metasedimentary interlayers. Based on the stratigraphy and geochemical characteristics, the Platreef at Tweefontein can be subdivided into the upper and lower Platreef. The upper Platreef subdivision occurs in the top 20-40 m of the sequence and is defined by higher Mg#, Cr, Cr (ppm)/MgO and Pt/Pd values compared to the lower Platreef. In addition, the majority of the grade and base metal sulphide (BMS) content is enriched in the upper versus the lower Platreef, particularly for the northern and central parts of Tweefontein. The upper and lower Platreef may have been derived from different magma sources based on the “R Factor” concept proposed by Campbell and Naldrett in 1979 whereby the abundance of the PGE relative to the BMS content is linked to the proportion of magma with which the sulphide ore equilibrated (Naldrett, 2005b). Previous detailed geochemical studies from Tweefontein Hill southwards highlighted compositional breaks in the Platreef sequence thought to represent distinct sill-like intrusions (Hutchinson and Kinnaird, 2005; Kinnaird, 2005; Manyeruke et al., 2005; Nyama et al., 2006). They reported a more primitive sill at the top of the Platreef, which correlates to the upper Platreef at Tweefontein. The lower Platreef is therefore likely to represent a different sill intrusion. A relatively homogenous pyroxenitic package characterises the upper Platreef, although a more heterogeneous package is observed close to and at Tweefontein Hill. At Tweefontein North, the base of the upper Platreef is often marked by a chromitiferous package comprising a pegmatoidal feldspathic pyroxenite unit, up to 6 m thick, capped by a chromitite layer. Due to similar stratigraphy and high PGE grades, this distinct horizon has been compared to the Merensky Reef found elsewhere in the Bushveld Complex. The predominant base metal sulphides (BMS) in the Platreef at Tweefontein are pyrrhotite, pentlandite, chalcopyrite with minor pyrite aligned with that found elsewhere along the Platreef strike. There is an increase in BMS content, primarily pyrrhotite, towards the base of the Platreef with massive and submassive sulphide development near the base and in the footwall, particularly at Tweefontein Hill. Sulphur isotopes and detailed mineralogical studies at Turfspruit have shown that the addition of S, As and Sb into the magma from the Duitschland footwall triggered the development of a PGE-poor sulphide liquid which was then able to mix, modify and dilute the magmatic sulphides (Hutchinson and McDonald, 2008). Due to the similarity in footwall between Turfspruit and Tweefontein, these proposed processes help to explain the increase in BMS towards the base and the development of basal massive and submassive sulphides, which are not necessarily associated with significant PGE grade. At Tweefontein North, the processes dominating the top-loaded PGE mineralisation were primarily magmatic. The PGM assemblage, hosted by base metal sulphides and magmatic silicates, is dominated by Pt-and Pd-bismuthides and -tellurides with minor PGE-sulphides and Pt-arsenides. PGE-sulphides occur in the Platreef where the chromitiferous horizon is developed, which may indicate an environment low in volatile activity and one of the most primary mineralisation styles along the Platreef strike. The footwall high, which separates the depressions at Tweefontein North and Tweefontein Hill may have kept the Platreef at Tweefontein North relatively protected from additional processes affecting Tweefontein Hill. In contrast, assimilation of the Duitschland footwall is thought to play a key role in the development of the variable but predominantly bottom-loaded PGE mineralisation at Tweefontein Hill. The PGM assemblage is Pd-dominant characterised by Sb-, As- and Bi-bearing PGM, reflecting the incorporation of Sb, As and Bi from the Duitschland footwall. The association of the PGE mineralisation with the extensive basal sulphide development implies that the mineralisation at Tweefontein Hill probably occurred due to the gravitational settling of a sulphide liquid containing a mix of sedimentary and PGE-hosting magmatic components. Due to a significant PGM-BMS association in the mineralised footwall and metasedimentary interlayers/xenoliths, a downward migrating sulphide melt is believed to be the main mechanism responsible for the redistribution of PGE, predominantly Pd, into the mineralised metasedimentary lithologies. Finally, the Platreef and footwall lithologies may be locally modified by late-stage felsic and hydrothermal fluids to form bismuthide- and arsenide-dominant PGM assemblages, primarily hosted in quartz and serpentine respectively. This study shows the PGM and sulphide mineralisation at Tweefontein to be multifaceted, involving magmatic processes, assimilation of the Duitchland footwall into the Platreef magma and late-stage hydrothermal and felsic fluid activity. Footwall composition and irregular floor topography, resulting in depression areas at Tweefontein North and Tweefontein Hill, are believed to play a key role in what processes become significant along the Tweefontein strike. This research represents a significant contribution to the understanding of the distinctly different PGE mineralisation styles at Tweefontein and allows for a complete comparison of the Platreef PGE mineralisation from Overysel to Turfspruit.