PhDENV (Geology) / Department of Mining and Environmental Geology / The study focused on the geology, structural setting and mineralisation of copper-sulphide deposits in the Musina area, located in the Central Zone of the Limpopo Mobile Belt of South Africa. The Messina copper deposits are located in the eastern part of Limpopo Province near the border with Zimbambwe. The deposits stretch from northeastern to southwestern direction for about 15 km. Previous copper mining in the area took place at Artonvilla, Messina, Harper, Campbell and Lilly copper deposits. The current study, however, focused on two main deposits, Campbell and Artonvilla. The origin, nature and mode of formation of the Cu-sulphide deposits in the Musina area have not been established with certainty. Two principal hypotheses on the origin of the Messina copper sulphide deposits have been proposed, viz; a magmatic-hydrothermal model, and meteoric waters model. Consequently, the mode of formation and mineralisation style of the Messina Cu-sulphide deposits remain contentious. Therefore, the main objective of the study was to investigate the nature and mode of formation of Cu-sulphide deposits in the Musina area. Different research methods have been applied in the current study so as to unpack the contradictory positions on the genesis of the Messina copper deposits. This included fieldwork, remote sensing data acquisition, laboratory work, and data analysis and interpretation. Fieldwork involved soil geochemical survey as well as rock and ore sampling within the study area. A total of 295 soil samples, 33 rock specimens and 21 ore samples were collected for laboratory investigation. Laboratory work consisted of a range of methods that included; geochemical analysis, petrographic and cathodoluminescence microscopy, ore mineralogy and ore microscopy, fluid inclusion geothermometry and isotope geochemistry. The work was done in different laboratories including: Mining and Environmental Geology Laboratory, Unviersity of Venda; Department of Geology Laboratory, University of Johannesburg; MINTEK Laboratory in Johannesburg; Société Générale de Surveillance Laboratory in Johannesburg, South Africa; Department of Applied Geology, Geoscience Institute, Göttingen University, Germany and Department of Geology, University of Georgia, Athens, United States of America. Remote sensing data was acquired from Southern Mapping Company, Johannesburg, South Africa. Interpretation of Remote sensing data was done at the University of Applied Sciences, Oswestfalen-Lippe, Germany. Data analysis and interpretation of laboratory results involved the use of: Desktop ArcGIS 10.4.1 for geochemical data interpretation; ENVI 5.1 and ArcGIS 10.4.1 Softwares for remote sensing data; and Triplot version 4.1.2 software for ternary plot for compositional variation of rocks. Soil geochemical survey revealed geochemical anomalies for Pb, Zn, Cu, As and Ni over the known copper deposits in the area as well as over six other areas that have not been associated with any sulphide mineralisation. Such new anomalous areas have been identified as target areas for future exploration of sulphide ore mineralisation. Petrographic studies of the rocks confirmed the host rocks to be amphibolite-quartz granulite, biotite-garnet-quartz granulite, amphibolite, quartzite, hornblende gneiss, quartzo-feldspathic gneiss, potassium-feldspathic gneiss and cal-silicate gneiss. These rocks were subjected to hydrothermal alteration during ore mineralisation within the area. It was further noted that epidote alteration was quite intensive in ore samples, while in unmineralised rock samples it was less intensive. Remote sensing data interpretation revealed spatial distribution and intensity of epidote alteration within the study area and in places coincided either with the known copper deposits or structural features, thus led to the identification of target areas for future mineral exploration in the Musina area. The current study established that the process of ore mineralisation in the Messina copper deposits took place in two distinct phases: first the formation of garnet, graphite, magnetite and hematite during regional metamorphism of the Limpopo Mobile Belt; and secondly, sulphide ore mineralisation resulting in the formation of copper ore comprising, veined, disseminated and brecciated ores. Sulphide ore mineralisation consisted mainly of pyrite, chalcopyrite, sphalerite, bornite, chalcocite and minor pyrrhotite and galena as well as traces of pentlandite, tennantite, mollybdenite, cobaltite and tetrahedrite. This confirms that the Messina copper deposits had complex sulphide ore mineralisation that is typical of hydrothermal mode of ore mineralisation from a magmatic source. The study further establishes the paragenitic sequence of ore mineralisation, comprising four stages: Stage I (Garnet- graphite – Fe oxides); stage II (Quartz- pyrite); stage III (Pyrite- sphalerite - chalcopyrite); and stage IV (Carbonates). Stage III represented the main stage of sulphide ore mineralisation in the area, while Stage IV comprising calcite, dolomite and ankarite marked the final stage of hydrothermal ore mineralisation. Paragenetic sequence identified three generations of quartz; first generation being associated with garnet, graphite, magnetite and hematite, second generation with pyrite and third generation with pyrite, sphalerite and chalcopyrite. Previous studies, however, indicated that there was only one generation of quartz that formed at the temperature between 210o to 150°C, but the current study established that the entrapment temperature of first generation quartz ranges from 315o to 200°C; second generation quartz from 235o to 135°C and third generation quartz from 240o to 115°C. At the same time, sulphur isotope investigation of chalcopyrite-pyrite pair from Campbell deposit registered a temperature of 359°C. The study therefore concluded that the temperature of ore formation within the Messina copper deposits ranged between 359°C and 115°C. The presence of halite and calcite as daughter minerals within the fluid inclusions was noted and this apparently is indicative of high salinity of fluid inclusions, which is considered as a product of direct exolution of crystalizing magma. Raman spectroscopy revealed the composition of gases in the fluid inclusions to be CH4 and N2 with 80% and 20% composition respectively, however, some inclusions were gas-poor. The presence of gases in the fluid inclusions is an indication that there was boiling at the time of entrapment. A narrow range of 34S values of -0.5 to 0.5‰ obtained in this study further confirms the magmatic source of Sulphur as Sulphur from the host rock was found to have high 𝛿34S value of 8.2‰. A genetic model for copper ore mineralisation within Musina area is proposed. The deposits are of polymetallic vein type that are genetically associated with porphyry copper deposits. According to this model, copper ore bodies were formed from hydrothermal fluids originating from magma and were epigenetic in nature. Geological structures in the area acted as conduits for hydrothermal fluids that resulted in the alteration of the host rocks and mineralisation of copper sulphide ore. Thus, the Messina coper deposits are of magmatic hydrothermal origin although the apparent location of a batholith is still unknown and the study recommends further viii research work on the location of the batholith that is presumed to have been the magmatic source. The study further recommend dating of later rocks as well as orebody s it is essential for understanding the process of ore formation in this area. For further exploration, areas that have undergone “moderate” to “high” degree of epidote alteration and lie in close proximity to geological structures such as faults and thrust folds that could have acted as conduits for hydrothermal fluids and resulted in sulphide ore mineralisation and registered high geochemical anomalies for Pb, Zn, As and Ni should be targeted. In support of further mineral exploration within the study area, the study recommend a detailed geostatistical application for the purpose of delineating homogeneous areas based on the combination of lineaments, interpolated soil geochemical maps and thematic maps. / NRF

The main magnetite seam of the Upper Zone of the Rustenburg Layered Suite (SACS, 1980) on the Bushveld Complex is known to host the world‘s largest vanadium bearing titaniferous iron ores. The vanadiferous titanomagnetites, contain vanadium in sufficient concentrations (1.2 - 2.2 per cent V₂O₅) to be considered as resources and vanadium has been mined historically by a number of companies among them Anglo-American, Highveld Steel and Vanadium and VanMag Resources as well as currently by Evraz Highveld Steel and Vanadium Limited of South Africa. The titanomagnetites contain iron ore in the form of magnetite and titanium with concentrations averaging 50-75 per cent FeO and 12-21 per cent TiO₂. The titaniferous iron ores have been historically dismissed as a source of iron and titanium, due to the known difficulties of using iron ore with high titania content in blast furnaces. The economic potential for the extractability of the titaniferous magnetites lies in the capacity of the ores to be separated into iron rich and titanium rich concentrates usually through, crushing, grinding and magnetic separation. The separatability of iron oxides and titanium oxides, is dependent on the nature in which the titanium oxide occurs, with granular ilmenite being the most favourable since it can be separated from magnetite via magnetic separation. Titanium that occurs as finely exsolved lamellae or as iron-titanium oxides with low titania content such as ulvospinel render the potential recoverability of titanium poor. The Upper Zone vanadiferous titanomagnetites contain titanium in various forms varying from discrete granular ilmenite to finely exsolved lamellae as well as occurring as part of the minerals ulvospinel (Fe₂TiO₄) and titanomagnetite (a solid solution series between ulvospinel and magnetite) . Discrete ilmenite constitutes between 3-5 per cent by volume of the massive titanomagnetite ores, and between 5-10 per cent by volume of the magnetite-plagioclase cumulates with more than 50 per cent opaque oxide minerals. The purpose of this research was to investigate the mineralogical setting and distribution of the iron and titanium oxides within the magnetitite layers from top to bottom as well as spatially along a strike length of 2 000m to determine the potential for the titanium to be extracted from the titanomagnetite ores. The titanomagnetites of the Upper Zone of the Bushveld Complex with particular reference to the Northern Limb where this research was conducted contains titanium oxides as discrete ilmenite grains but in low concentrations whose potential for separate economic extraction will be challenging. The highest concentration of titanium in the magnetite ores is not contained in the granular ilmenite, but rather in ulvospinel and titanomagnetite as illustrated by the marked higher concentration of TiO₂ in the massive ores which contain less granular ilmenite in comparison to the disseminated ores which contain 3 to 8 percentage points higher granular ilmenite than the massive ores. On the scale of the main magnetite seam, the TiO₂ content increases with increasing stratigraphic height from being completely absent in the footwall anorthosite. The V₂2O₅ content also increases with stratigraphic height except for in one of the 3 boreholes where it drops with increasing height. The decrease or increase patterns are repeated in every seam. The titanomagnetites of the main magnetite seam display a variety of textures from coarse granular magnetite and ilmenite, to trellis ilmenite lamellae, intergranular ilmenite and magnesian spinels and fine exsolution lamellae of ulvospinel and ferro-magnesian spinels parallel to the magnetite cleavage. The bottom contact of the main magnetite seam is very sharp and there is no titanium or vanadium in the footwall barely 10cm below the contact. Chromium is present in the bottom of the 4 layers that constitute the main magnetite seam and it upwards decreases rapidly. In boreholes P21 and P55, there are slight reversals in the TiO₂ and V₂O₅ content towards the top of the magnetite seams.