Thesis (MTech. degree: Chemistry) / Trace and ultra-trace levels of platinum group metals (PGMs) in waste effluent pose an increasing risk of exposure to human and aquatic organisms. These metal ions accumulate in environmental matrices such as water, soil and sediments thereby aggravating the situation. In addition, industrial and automotive catalytic emissions of PGMs are increasing worldwide and both mechanical and thermal wear have been found to increase the risk of exposure. Currently, methods for the determination of low levels (μg/L) of PGMs require expensive and sophisticated instrumentation. The objective of this study was to investigate the type of bonding that would lead to preconcentration of low levels of Pt, Pd and Rh ions onto suitable solid phase adsorbents, allowing for the monitoring of their possible presence in river water samples taken downstream of platinum refineries. Preconcentration prior to analysis will enable the metal ions of interest to be determined on a less expensive instrument, such as an Flame Atomic Absorption Spectrometer, Electro Thermal Atomic Absorption Spectrometer, or at most, by use of Inductively Coupled Plasma-Optical Emission Spectrometry. Different solid phase extraction methods were applied including maize tassel, four commercially available resins and two modified resins. Results, particularly for the adsorption of Pt, were excellent with up to twenty two times the original concentration of this metal ion being recovered.

Philosophiae Doctor - PhD / Nowadays, the pollution of surface waters with chemical contaminants is one of the most crucial environmental problems. These chemical contaminants enter rivers and streams resulting in tremendous amount of destruction, so the detection and monitoring of these chemical contaminants results in an ever-increasing demand. This thesis describes the search for a suitable method for the determination of platinum group metals (PGMs) in environmental samples due to the toxicity of mercury films and the limitations with methods other than electroanalytical methods. This study focuses on the development of a novel bismuth-silver bimetallic nanosensor for the determination of PGMs in roadside dust and soil samples. Firstly, individual silver, bismuth and novel bismuth-silver bimetallic nanoparticles were chemically synthesised. The synthesised nanoparticles was compared and characterised by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), ultraviolet-visible spectroscopy (UV-Vis), Fourier-transformed infrared spectroscopy (FT-IR), Raman spectroscopy, and transmission electron microscopy (TEM) analysis to interrogate the electrochemical, optical, structural, and morphological properties of the nanomaterials. The individual silver, bismuth, and bismuth-silver bimetallic nanoparticles in the high resolution transmission electron microscopy results exhibited an average particle size of 10-30 nm. The electrochemical results obtained have shown that the bismuth-silver bimetallic nanoparticles exhibit good electro-catalytic activity that can be harnessed for sensor construction and related applications. The ultraviolet-visible spectroscopy, Fourier-transformed infrared spectroscopy, and Raman spectroscopy results confirmed the structural properties of the novel bismuth-silver bimetallic nanoparticles. In addition the transmission electron microscopy and selected area electron diffraction morphological characterisation confirmed the nanoscale nature of the bismuth-silver bimetallic nanoparticles. Secondly, a sensitive adsorptive stripping voltammetric procedure for palladium, platinum and rhodium determination was developed in the presence of dimethylglyoxime (DMG) as the chelating agent at a glassy carbon electrode coated with a bismuth-silver bimetallic nanofilm. The nanosensor further allowed the adsorptive stripping voltammetric detection of PGMs without oxygen removal in solution. In this study the factors that influence the stripping performance such as composition of supporting electrolyte, DMG concentration, deposition potential and time studies, and pH have been investigated and optimised. The bismuth-silver bimetallic nanosensor was used as the working electrode with 0.2 M acetate buffer (pH = 4.7) solution as the supporting electrolyte. The differential pulse adsorptive stripping peak current signal was linear from 0.2 to 1.0 ng/L range (60 s deposition), with limit of detections for Pd (0.19 ng/L), Pt (0.20 ng/L), Rh (0.22 ng/L), respectively. Good precision for the sensor application was also obtained with a reproducibility of 4.61% for Pd(II), 5.16% for Pt(II) and 5.27% for Rh(III), for three measurements. Investigations of the possible interferences from co-existing ions with PGMs were also done in this study. The results obtained for the study of interferences have shown that Ni(II) and Co(II) interfere with Pd(II), Pt(II) and Rh(III) at high concentrations. The interference studies of Cd(II), Pb(II), Cu(II) and Fe(III) showed that these metal ions only interfere with Pd(II) and Pt(II) at high concentrations, with no interferences observed for Rh(III). Phosphate and sulphate only interfere at high concentrations with Pt(II) and Rh(III) in the presence of DMG with 0.2 M acetate buffer (pH = 4.7) solution as the supporting electrolyte. Based on the experimental results, this bismuth-silver bimetallic nanosensor can be considered as an alternative to common mercury electrodes, carbon paste and bismuth film electrodes for electrochemical detection of PGMs in environmental samples. Thirdly, this study dealt with the development of a bismuth-silver bimetallic nanosensor for differential pulse adsorptive stripping voltammetry (DPAdSV) of PGMs in environmental samples. The nanosensor was fabricated by drop coating a thin bismuth-silver bimetallic film onto the active area of the SPCEs. Optimisation parameters such as pH, DMG concentration, deposition potential and deposition time, stability test and interferences were also studied. In 0.2 M acetate buffer (pH = 4.7) solution and DMG as the chelating agent, the reduction signal for PGMs ranged from 0.2 to 1.0 ng/L. The detection limit for Pd(II), Pt(II) and Rh(III) was found to be 0.07 ng/L, 0.06 ng/L and 0.2 ng/L, respectively. Good precision for the sensor application was also obtained with a reproducibility of 7.58% for Pd(II), 6.31% for Pt(II) and 5.37% for Rh(III), for three measurements. In the study of possible interferences, the results have shown that Ni(II), Co(II), Fe(III), Na+, SO42- and PO43- does not interfere with Pd(II) in the presence of DMG with sodium acetate buffer as the supporting electrolyte solution. These possible interference ions only interfere with Pt(II) and Rh(III) in the presence of DMG with 0.2 M acetate buffer (pH = 4.7) as the supporting electrolyte solution.

M.Tech. / The Inductively Coupled Plasma Mass Spectrometry (ICP-MS) technique showed very high uncertainties associated with the determination of the concentrations of minor elements in the Platinum Group Metal (PGM) smelting plant samples. This project reports on the work done for the identification of, and subsequent minimisation of the sources of uncertainties associated with the measurements of minor elements in the PGM Furnace Matte material by ICP-MS. To perform these studies, Elan 6000, Shimadzu ICPM-8500 and Finnigan Element 2 ICP-M spectrometers were employed. Synthetic Furnace Matte samples (SFMSs) were prepared and used to ascertain the uncertainties associated with the alleged sources at Mintek and Leo-Tech laboratories. The Element 2 spectrometer dominated the other two ICP-M spectrometers in terms of the accuracy for the determination of the concentrations of minor elements in SFMSs. The evidence of spectral interferences from the significant deviations in the measurement results between the isotopes of the same element was observed in the quantification of Zn, Se, Te and Sn in SFMS by the quadrupole Elan 6000 and the Shimadzu spectrometers. It also transpired that the accuracy of the quantitative determination of minor elements in the Furnace Matte (FM) matrix by ICP-MS was hampered by the matrix elements with the severity depending on the specific analyte and the make and model of the ICP-M spectrometer. The Anglo platinum FM material that was analysed in the second round robin was used as a Certified Reference Material (CRM) in the analysis of the Lonmin FM sample. It was revealed that the laboratory standard operating procedures for the preparation, dilution and subsequent analysis of the sample are potential sources of uncertainty in measurement results. The two-fold dilution of the sample for the lessening of the matrix effects was not effective. The use of multi-walled nanotubes for the alleviation of the matrix effects by removal was also not successful. Nevertheless standard addition method (SAM), combined with internal standardisation can be used as an effective calibration method in ICP-MS to achieve less matrix interfered results over the combination of the common external standardisation and internal standardisation methods.

Please read the abstract in the section 00front of this document / Thesis (PhD)--University of Pretoria, 2009. / Geology / unrestricted

This research describes a two-dimensional modelling effort of heat and mass transport in simplified intrusive models of sills and their feeder dykes. These simplified models resembled a complex intrusive system such as the Great Dyke of Zimbabwe. This study investigated the impact of variable geometry to transport processes in two ways. First the time evolution of heat and mass transport during cooling was investigated. Then emphasis was placed on the application of convective scavenging as a mechanism that leads to the formation of minerals of economic interest, in particular the Platinum Group Elements (PGEs). The Navier-Stokes equations employed generated regions of high shear within the magma where we expected enhanced collisions between the immiscible sulphide liquid particles and PGEs. These collisions scavenge PGEs from the primary melt, aggregate and concentrate it to form PGEs enrichment in zero shear zones. The PGEs scavenge; concentrate and 'glue' in zero shear zones in the early history of convection because of viscosity and dispersive pressure (Bagnold effect). The effect of increasing the geometry size enhances scavenging, creates bigger zero shear zones with dilute concentrate of PGEs but you get high shear near the roots of the dyke/sill where the concentration will not be dilute. The time evolution calculations show that increasing the size of the magma chamber results in stronger initial convection currents for large magma models than for small ones. However, convection takes, approximately the same time to cease for both models. The research concludes that the time evolution for convective heat transfer is dependent on the viscosity rather than on geometry size. However, conductive heat transfer to the e-folding temperature was almost six times as long for the large model (M4) than the small one (M2). Variable viscosity as a physical property was applied to models 2 and 4 only. Video animations that simulate the cooling process for these models are enclosed in a CD at the back of this thesis. These simulations provide information with regard to the emplacement history and distribution of PGEs ore bodies. This will assist the reserve estimation and the location of economic minerals.

The selective recovery of rhodium from wastewaters, in which the metal would be otherwise lost, would be highly profitable if the process were suitably low-cost. Current recovery processes are generally high maintenance and high-cost, whereas biological processes can be engineered to run with little external input in terms of cost and maintenance. Three emerging technologies were chosen based on their reported efficiency when removing base metals from wastewaters. The first technology screened, the sulphide-extraction membrane bioreactor (SEMB), consists of a sulphate-reducing prokaryote (SRP) anaerobic digester, in which a silicone membrane is submerged. Wastewater is passed through the membrane and metal ions are precipitated as metal sulphides by the hydrogen sulphide gas, which is capable of permeating the membrane. The second technology screened was a fluidized sand bed reactor in which metal ions are removed from solution via induction of nucleated precipitation by sodium carbonate onto the sand grains. The third, and most well established removal technology screened was a biosorption system using immobilized Saccharomyces cerevisiae biomass as the biosorbent. Experimental trials with each technology highlighted drawbacks with each; the SEMB system proved to be largely ineffective when challenged with the removal of rhodium from the wastewater as the rhodium precipitate fouled the membrane within hours, the fluidized bed system seemed unable to overcome the acidity of the wastewater and thus could not precipitate out the rhodium metal, and the efficiency of the biosorption process was hampered by the diversity of rhodium species present in the wastewater, which reduced the amount recovered. The outcomes of the trials with each technology indicated that further optimization of the technology or pretreatment of the wastewater is necessary before any of these options can be implemented. It could be concluded, however, that despite further optimization, both the SEMB and the fluidized bed system were not applicable in this case as precipitation would be non-specific, resulting in the necessity for further steps in order to purify the rhodium ions. Hence, the biosorption system was shown to be most applicable, and further optimization of the system could yield a highly efficient rhodium recovery process.

Please read the abstract in the section 00front of this document / Thesis (PhD)--University of Pretoria, 2006. / Geology / Unrestricted

>Magister Scientiae - MSc / The Platreef is known for its complexity and its heterogeneous lithologies, coupled with an unpredictable PGE and BMS mineralisation. The motivation behind this study was to aid mining geologists in targeting mineralisation irrespective of the farm. It is known that the Platreef generally overlies different footwall lithologies at individual farms. Thus, the aims of this study were firstly to investigate the potential of chemostratigraphy by delineating indices indicative of distinctive lithological layers. These indices were then tied to the second aim; which were to use geochemical vectoring, which is process-based, to target the PGEs at two different farms. This study included three drillcores: from the farms Sandsloot (SS339) and Tweefontein (TN754 and TN200). The footwall units at Tweefontein are shales of the Duitschland Formation and the Penge banded iron formation; and at Sandsloot it is the Malmani Subgroup dolomites. Samples included 121 quarter cores, used for petrographical and geochemical studies. The elemental rock composition was determined by XRF and ICP-OES analyses. The approach also included statistical and mass balance methods to understand the geological and geochemical controlling processes. Initially, the Platreef package at both farms was petrographically divided into three main layers: pyroxenite, and two distinctive feldspathic pyroxenites (FP-I and FP-II). However, the pyroxenites were also further separated as P-I and P-II, because of a higher notable difference in the degree of alteration within P-I. Progressive degrees of metasomatism were further observed in the lithologies, e.g. within the Platreef package, where feldspathisation was potentially the main metasomatic process. Many geochemical plots (corroborated by the petrographical and mass balance results) illustrated that the feldspathisation were linked to an increase in the content of Al₂O₃ and CaO, and coupled with a decrease in content of Fe₂O₃ and MgO. Together with other geochemical trends, geochemically distinct units of the Platreef package could be discriminated with a metasomatism index (MI; CaO + 10Na₂O / CaO + 10Na₂O + Fe₂O₃ + MgO). The ensuing MI is lowest for the P-II pyroxenite and shows a progressive increase through FP-I, P-I to the highest values in FP-II. Geochemical layering were also observed in the calcsilicates and hornfels; e.g. a progressive decrease in the content of Fe₂O₃, Al₂O₃, Ce, Co, Cu, Ni, Zn, Zr, Au, Pd and Pt from the hornfels subunits H-I, H-II to H-III and an increase in of SiO₂, Fe₂O₃, TiO₂, SO₃, Co, Cu, Ni, Rb, V and Zn content from CS-I, CS-II to CS-III. Correlating the pyroxenites and feldspathic pyroxenites spatially from one drillcore to another were hindered, hence, chemostratigraphy were not completed. In terms of vectoring, it was essential to establish a possible link between the metasomatism index and the nature and style of the PGE and/or BMS mineralisation. The Hornfels subunit H-I and calcsilicate subunit CS-III were the main carriers of BMS and PGE. The Platreef package were more complicated: P-I (low PGE, low BMS); P-II (low PGE, high BMS); FP-II (high PGE, low BMS); and FP-I (high PGE, high BMS). Element indices (e.g. Cu+Ni and Co+Zn) were developed to define a consistent gradient indicative of these ore subunits. A validation process to assess the metasomatism index (MI), base metal indices and PGE distribution within the individual drillcores (TN754, TN200 and SS339) were then undertaken. The results were that the MI ranges were similar in all drillcores, and discriminated the subunits of the Platreef package, gabbronorites and even the calcsilicates. The base metal ratios (e.g. Ni/Co and Cu/Co) were indicative of the PGE rich zones. Trends of the base metal ratios reflected a strong positive relationship with the MI within the Platreef package and the calcsilicates. However, the opposite trend is observed with the hornfels. In conclusion, the MI could potentially be a strong vector of high PGE and BMS mineralisation. It is also possible to discriminate lithologies within the Platreef package with the MI. However, it should be noted that the limitation of this study is that the results are based on three drillcores. The Platreef is heterogeneous at individual farms and extremely diverse across the northern limb. Therefore, future research could be undertaken to validate these findings, by using a bigger drillcore database. / National Research Foundation

No description available.

Thesis (M.Sc. (Geology)) -- University of Limpopo, 2022 / The Two Rivers Platinum Mine (TRP) located in the Eastern Bushveld Igneous Complex is currently exploiting platinum-group elements (PGE) in the Upper Group 2 chromitite (UG2) Reef at the Dwarsrivier Farm. TRP has acquired a new prospect (at the Buffelshoek Farm) and is currently planning to mine the UG2 Reef and potentially also the Merensky Reef (MR). Three drill-cores which intersected the UG2 Reef and MR at the Buffelshoek Farm made available by TRP were sampled for mineralogical studies using complementary techniques including reflected light microscopy, mineral liberation analyser and electron microprobe. The platinum group minerals (PGM) which host the PGE exhibit variability in their flotation rates and consequently variable PGE recoveries that is mostly attributed to the not so well understood PGM distributions and characteristics. The purpose of the study was to investigate the PGE process mineralogical characteristics such as the PGM phases, their modal abundances and mineral associations, as well as the grain size distributions within the UG2 Reef and MR at the Buffelshoek Farm. The observed PGM phases are broadly grouped into PGE sulphides, PGE arsenides, PGE bismuth-tellurides, PGE antimonides and PGE alloys. The PGM phases are largely dominated by PGE-sulphides (average of 80%) in the UG2 Reef and PGE-arsenides (average of 39%) in the MR. Although the UG2 Reef and MR are mineralogically different, the PGM observed are similar in composition, but vary in their proportions. The PGM are mostly associated with base metal sulphides typically, pentlandite in the UG2 Reef and silicates, which are dominated by amphiboles in the MR. The PGM grain sizes generally range between 2 and 22 microns in the UG2 Reef and range between 2 and 32 microns in the MR. The concentrations of platinum are the highest in both the UG2 Reef and MR, and with the platinum largely deported in PGE-sulphides (about 69 - 84.9%) in the UG2 Reef and PGE-arsenides in the MR. Palladium is mostly deported in the PGE sulphides (about 52.3 - 69.2%) in the UG2 Reef and mostly deported in PGE antimonides (about 43%) and PGE bismuth-tellurides (about 37%) in the MR. Rhodium (Rh) is entirely deported in the PGE sulphides in the UG2 Reef and deported in PGE sulphides (about 86.5%) and PGE bismuth-tellurides (about 13.5%) in the MR. Expected recoveries of PGM ranges from 76 to 89% for PGE sulphides and arsenides in the UG2 Reef and 61.3% in the MR, which is considered good. PGE bismuth-tellurides, PGE antimonides and PGE alloys are expected to be variably to poorly recovered, requiring suitable reagents to be well recovered both in the UG2 Reef and MR. / Faculty of Science and Agriculture Research Division Geological Society of South Africa North West University's School of Geo- and Spatial Science