Student Number : 0201438A - PhD thesis - School of Geosciences - Faculty of Science / This project focuses on the Upper Critical and Lower Main Zones in the eastern Bushveld Complex, South Africa. Lithological and stratigraphic information show that there are distinct differences at this level between the eastern and western limbs of the complex. Geochemical studies are centred on the Merensky and Bastard Cyclic Units in which the platiniferous Merensky Reef occurs. A major geochemical hiatus occurs in the Bushveld Complex at the level of the platiniferous Merensky Reef, close to the Critical/Main Zone boundary. The origin of this hiatus and its relation to mineralisation has not been fully resolved. Geochemical parameters are investigated that allow minerals in the Merensky and Bastard Cyclic Units to be classified as originating from either Critical or Main Zone magmas. Modelling of element ratios (Ni/Y, Cr/Ni, Cr/Co, Y/Co, Cr/V, Co/V and Cr/MgO) demonstrates the varying reliability of using ratios as geochemcial tools to constrain magma influxes within a chamber. However, it is shown that the Cr/MgO ratio is effective in determining real differences across the Critical/Main Zone boundary that are independent of lithology. In addition, initial Sr isotope ratios for plagioclase are significantly different in Critical and Main Zone rocks. Geochemical data through the Merensky and Bastard Cyclic Units indicate that orthopyroxene that originated from magma with composition like that of the Critical Zone magma sometimes occurs together with plagioclase that originated from Main Zone magma. In detail, in the pyroxenite at the base of the Merensky Unit, both plagioclase and orthopyroxene display Critical Zone signatures, but in the overlying part of the Merensky Cyclic Unit, plagioclase increasingly shows a Main Zone signature, whereas orthopyroxene continues to display a Critical Zone signature. Similarly, in the Bastard pyroxenite, Sr isotopes and absolute Sr in plagioclase display a range of values from Main Zone to Critical Zone, but orthopyroxene consistently displays Critical Zone affinity. These observations of mineral disequilibrium clearly show that the two major minerals in the Merensky and Bastard Cyclic Units were formed from two different, but coexisting, magmas. A model that accounts for this disequilibrium is proposed here. It invokes the influx of Main Zone magma at the level of the base of the Merensky unit that dispalced the Critical Zone magma upward, but the two magmas did not mix. The latter continued to crystallise orthopyroxene which sank through the Main Zone influx, due to its density contrast. These crystals collected on the crystal pile to form the Merensky pyroxenite. The Main Zone magma, into which the cumulus Critical Zone orthopyroxene accumulated, crystallised interstitial plagioclase that had a Main Zone Sr isotopic ratio. Whole-rock, major element geochemical data show that a variable proportion of the plagioclase in both the Merensky and Bastard pyroxenites is cumulus. It is inferred to have accumulated with orthopyroxene and has a Critical Zone initial Sr isotope ratio. Thus the two pyroxenites now yield a mixed Sr isotopic signature of Critical Zone cumulus and Main Zone intercumulus and possibly cumulus plagioclase that varies along strike. Above the two pyroxenites, the Sr signature of the norites and anorthosites of both cyclic units is dominated by cumulus plagioclase from the Main Zone magma. It is concluded that the variations in initial Sr isotope ratios do not result from mixing of magmas, but result from accumulation of orthopyroxene and plagioclase from a higher, isotopically distinct layer of magma into an underlying layer. The Merensky and Bastard Cyclic Units therefore display features of Critical or Main Zone magma characteristics depending upon which chemical parameter is considered. These cycles are therefore classified as a Transitional Unit.

Evidence of mineral disequilibrium is presented for the Merensky Reef at Winnaarshoek in the eastern Bushveld Complex. Petrographic disequilibrium textures, disequilibrium in orthopyroxene, plagioclase and clinopyroxene mineral compositions as well as disequilibrium in Sm-Nd isotopic compositions of whole rock samples and coexisting plagioclase and orthopyroxene are presented. Disequilibrium textures presented include clinopyroxene exsolution lamellae in orthopyroxene; resorbed plagioclase in orthopyroxene or relict plagioclase; various inclusions such as orthopyroxene, plagioclase or clinopyroxene in larger oikocrysts of clinopyroxene or orthopyroxene; discontinuous rims of clinopyroxene surrounding orthopyroxene; resorbed orthopyroxene in clinopyroxene; and corona textures associated with olivine. These textures were used to derive a possible mineral crystallization sequence. At least two sequences of crystallization took place, both of which crystallized plagioclase first. One sequence then crystallized olivine which was then consumed to produce orthopyroxene which crystallized prior to late clinopyroxene. The other sequence indicates orthopyroxene crystallization after plagioclase crystallization, followed by crystallization of clinopyroxene. These sequences indicate at least two magmas were responsible for the genesis of the Merensky Reef and its hanging wall and footwall units. Compositionally, disequilibrium is evident in the range of compositions found in coexisting orthopyroxene, plagioclase and clinopyroxene with stratigraphic height, with particular reference to the change in mineral composition in each of the hanging wall, Reef and footwall units. Orthopyroxene compositions range in Mg numbers between 74.6 and 82.9 (77.4) in the hanging wall, 78.5 and 87.0 (avg. 81.1) in the Reef, and 77.9 and 84.1 (avg. 81.3) in the footwall. Plagioclase compositions range in An content between An64.9 and An82.3 (avg. An75.1) in the hanging wall, An56.8 to An70.8 (avg. An62.7) in the Reef, and An54.2 to An86.3 (avg. An73.2) in the footwall. In terms of Sm-Nd isotopic compositions, disequilibrium is evident between both whole rock samples and coexisting plagioclase and orthopyroxenes. Bulk rock Sm-Nd isotopic compositions show a range in ԐNd values between ԐNd (2.06 Ga) = -4.8 to -6.4 in the hangingwall, ԐNd (2.06 Ga) = -6.3 to -8.5 in the Reef, and ԐNd (2.06 Ga) = -4.5 to -6.3 in the footwall. Similar ԐNd values are present in the hanging wall and footwall units, with a clear “spike” in the Merensky Reef. ԐNd values in plagioclase are between ԐNd (2.06 Ga) = -5.8 and -7.8, while orthopyroxene isotopic Sm-Nd values are between ԐNd (2.06 Ga = -7.1 and -9.1. The mineral disequilibrium features presented within this study help elucidate the crystallization sequence of the magma as well as to constrain the contamination of the magma upon ascension and emplacement of the Merensky Reef. The results of this study favour a model where a mantle plume resulted in the ascent of a new magma which was contaminated by the assimilation of old, lower crust. Contamination took place prior to the possible lateral emplacement of the Merensky reef as a density current. 5-10% contamination of depleted mantle or a B2-“like” source by Archaean TTGs is modeled to achieve the contamination “spike” of ԐNd = -8.5 in the Merensky Reef.

Magister Scientiae - MSc (Earth Science) / This study area is situated within the Eastern Bushveld complex at Dwarsrivier chrome mine, which is approximately 30 km from Steelpoort and 60km from Lydenburg in the Mpumalanga province. The primary aim of the project is to identify the petrological and geochemical characteristics that can be used to distinguish the various rock types of feldspathic pyroxenites, chromitites, anorthosites and chromitite pyroxenites and determine whether the various rock types are from the MG2 package and MG3 package were formed from a single or multiple magma pulses. The geochemical and mineralogical variation studies were carried out using cores from borehole DWR74 and DWR172 located on the farm Dwarsrivier 372 KT. Using the combination of various multivariate statistical techniques (factor, cluster and discriminant analysis) multi element diagrams and trace element ratios, the outcome of the study demonstrated that each of the four rock types can be sub-divided into two groups.

M. Tech. (Department of Metallurgical Engineering, Faculty of Engineering Technology), Vaal University of Technology. / Lonmin mining company located in the Bushveld Complex of South Africa is one of the main platinum group elements (PGEs) producers in the world. Its core operations are made up of 11 shafts and inclines. There are resources of 181 million troy ounces of 3PGE + Au, and there are reserves of 32 million ounces of 3PGE + Au. One of the ore type produced at Lonmin is UG2 ore which is dominated by the high presence of chromite. The UG2 ore is also associated with PGE assemblages divided into sulphides and non-sulphides, and it is beneficiated through the froth flotation technique. Froth flotation is a physico-chemical process that is used for separation of desired valuable minerals from the gangue minerals by utilising the difference in surface properties. The process has been achieving lower recoveries with P4 (shaft name) UG2 ore compared to Eastern Platinum Limited (EPL) UG2 ore when using similar reagents suite, this leads to loss of valuable minerals to the tailings, both ores were from Lonmin. The first step was to conduct the mineralogical analysis conducted using Scanning electron microscopy- energy dispersive spectroscopy (SEM-EDS), X-ray diffraction (XRD), and optical microscopy to study the mineral composition of the two ores, and to identify any differences between them (two ores) considering that EPL UG2 ore is a blend of P1, P2, P3 (shaft names) and P4 UG2 ores while P4 UG2 ore is not blended with any other ores. The mineralogical results showed the presence of chromite, plagioclase, enstatite and sulphide minerals. The PGEs could not be detectable by any of the techniques used due to their small size and rarity. However, X-ray diffraction detected differences in concentrations of minor gangue constituents such as talc, muscovite, chlorite and actinolite and these results suggest that reagent consuming gangue mineralogy may have contributed to the differences in PGE recoveries by flotation. Batch flotation tests were also conducted. The existing reagent suite consisted of CuSO4 as an activator, Sodium n-propyl xanthate (SPNX) as a collector, carboxymethyl cellulose CMC as a depressant, and Senfroth 200 as a frother, and this was a single collector system. Therefore it was imperative to conduct flotation n investigation on alternative collector blends in order to improve the recovery of P4 UG2 ore. SNPX was used as the primary collector and it was blended with the following co-collectors: alkyl dithiocarbamates (DTC), two formulations of S-alkyl-N-butyl thionocarbamates (ABTC C1 & ABTC C2), and two formulations O-isopropyl-N-ethyl thionocarbamate (IPETC 30 & IPETC 31), one co-collector at a time. The first test incorporated the SNPX at dosage of 150 g/t without a blend and this dosage was selected based on the current optimum practice used at Lonmin and to use as a benchmark for the project. Trying to maintain the same dosage of 150 g/t of collectors, SNPX + co-collector were blended at two different dosages of 100 g/t + 50 g/t, and was also due to the fact that the co-collectors were highly concentrated and small dosages were expected to perform very well with SNPX. Lastly, the SNPX + co-collector at dosages 100 g/t + 125 g/t, here the dosage of co-collector was very high compared to 50 g/t and this was to check the effect of high dosages of highly concentrated collectors on the performance of the ore. The flotation results showed that the use of 50 g/t of co-collectors yielded optimum PGEs + Au recoveries and grades, while the dosage of 125 g/t decreased recoveries and grades. The high dosage quantities of collectors do not necessarily mean they will yield improved recoveries and grades. Different chain structures can be used to alter the behaviour of a collector, and these may increase or decrease their capabilities to cause higher recoveries. By using a collector with a longer hydrocarbon chain the flotation limit may be extended without loss of selectivity, consequently bringing about greater water repulsion, instead of increasing the concentration of a shorter chain collector. At 100 g/t of SNPX and 50 g/t of co-collector i.e. SNPX + IPETC 30 yielded improved 3PGE + Au recovery of 85.7 % at 3PGE + Au grades of 60.14 g/t, compared to the unblended SNPX (150 g/t) which yielded 3PGE + Au recovery of 81.1 % but insignificantly higher grade of 60.53 g/t. On the other hand, SNPX + IPETC C1 blend yielded low 3PGE + Au recoveries compared to SNPX + IPETC 30 and SNPX + IPETC 31 blends, but it achieved the highest grade of 76.1 g/t. Evidently, this proves that the relationship between recovery and grade is a trade-off. The results have also shown the synergic effects, especially for SNPX blended with IPETC 30, and SNPX blended with IPETC 31 at dosage of 100 g/t (SNPX) and 50 g/t (IPETCs). It can be concluded that the different interaction obtainable from the thionocarbamate (ROCSNHR), effectively complement that from the xanthate ion (ROCS2–) to achieve more collector interaction at surface sites otherwise interactable for xanthate only. Therefore the collector blends rendered the mineral of interest hydrophobic and as a result the minerals were recovered to the concentrate. On the other hand, too much of collectors may not be beneficial. At the dosage of 100 g/t of SNPX and 125 g/t of collectors, SNPX + DTC attained lower recoveries compared to SNPX, SNPX + IPETC 30, SNPX + IPETC 31, however the grade was higher than achieved SNPX + IPETC 30, SNPX + IPETC 31 and SNPX + ABTC C1. Nevertheless, comparing these results to the dosage of 50 g/t of the co-collectors, the 125 g/t did not perform well at all. The dosage of 125 g/t of co-collectors lead to loss of collecting power and selectivity, especially for SNPX + IPETC 30, SNPX + IPETC 31, and SNPX + ABTC C1 blends. It is therefore wise to conduct an optimisation test to determine the correct dosing rate. In addition, the chromite entrainment was below the smelter limit and is very beneficial since chromite is detrimental to the furnace. Therefore, it is concluded that the blends of SNPX with IPETC 30 and IPETC 31 at a dosage 50 g/t have shown satisfying recoveries and the FeCr2O4 recovery is less than 1 % meaning there will not be any smelter penalties for FeCr2O4 content. Therefore, these are the recommended collector blends. It is recommended that further mineralogical study of the ores be conducted so that it may provide deeper insight into the causes of low recoveries under SNPX only. The system of blended collectors and its optimisation would be beneficial and can be practiced. The Chemisorption studies between the minerals and co-collectors used will provide more specific insight and details into the actual interaction synergy that gave the improved recoveries.