In this study the unique Magotteaux Mill® system was used to control the grinding chemical conditions, which may be adjusted by varying grinding media, purging gas and pH, during grinding. An electrochemical apparatus was used to investigate oxidation-reduction behaviour of grinding media and sulphide mineral electrodes, as well as their galvanic interaction in-situ of the Magotteaux Mill®. Galvanic interaction between the grinding media (mild steel, 15% chromium, 21% chromium and 30% chromium media) and the sulphide minerals (bornite, arsenopyrite and pyrite) was initially quantified in-situ of the mill by electrochemical techniques under different grinding atmospheres (nitrogen, air and oxygen). An innovative mathematical theoretical model was developed to describe the effect of galvanic interaction on oxidation rates of the grinding media during grinding, which was verified by the experimental data. Galvanic interaction enhanced the oxidation of the grinding media and produced more oxidized iron species in the mill discharge. It was observed that oxidized iron species (EDTA extractable iron) was linear with galvanic current between the grinding media and the sulphide minerals, in agreement with the prediction of the theoretical model. The effect of grinding conditions on pulp chemistry, surface properties and floatability was investigated by the measurement of dissolved oxygen (DO), pH, pulp potential (Eh), ethylene diamine-tetra acetic acid (EDTA) extraction, X-ray photoelectron spectroscopy (XPS) and floatation recovery. / PhD Doctorate

Thesis (MSc. (Physics)) --University of Limpopo, 2009 / Calculations were carried out on transition-metal sulphides (TMS) and transitionmetal arsenides (TMA), in both pyrite- and marcasite-type structures, using planewave (PW) pseudopotential methods within density functional theory (DFT) in the local density approximation (LDA). The structural, electronic and optical properties for both pyrite- and marcasite-type structures (naturally occurring and converted) have been investigated. The equilibrium lattice parameters were investigated and are in good agreement with the experimental values. The heats of formation calculations predict that the naturally occurring pyrite- and marcasite-type structures are more stable than the converted ones. In particular, the calculated pyrite-type RuS2 compares well to the experimental value (with energy difference of 0.381 eV/atom). The bulk modulus and elastic properties were calculated. The predicted anisotropic ratio shows that the naturally occurring pyrite- and marcasite-type structures are more stable than the converted ones. Moreover, the electronic density of states and band structure calculations reveal that most compositions shows semiconducting behaviour except for the converted pyritetype structures, i.e OsAs2 and RuAs2 where a metallic behaviour was observed. The electronic charge density and charge density difference show charge accumulation on bonding atoms, predicting the charge gain/ loss and nature of bonding to be covalent/ weak ionic between the atoms. Lastly, optical properties are computed at equilibrium and predict that naturally occurring structures have lower absorption and reflectivity than the converted structures. At different pressures ranging from -10 GPa to 10 GPa, the absorption and reflectivity spectra show a shift from the 0 GPa spectrum for all the structures / National Research Foundation

The Bien Venue massive sulphide deposit is associated with a felsic volcanic succession developed in the north-eastern part of the Barberton Greenstone Belt, Eastern Transvaal. The deposit is situated 8km east-north-east of Louw's Creek between the Lily Syncline to the south and the Stentor Pluton to the north. The stratigraphy of the Onverwacht, Fig Tree and Moodies Groups in the vicinity of the deposit is poorly documented, and the exact stratigraphic position of the host felsic volcanics is not known. They are tentatively correlated with the felsic volcanics from the Theespruit Formation, Onverwacht Group. The felsic volcanics have undergone low-grade greenschist facies metamorphism and occur as quartz-sericite schists. Detailed petrography enables sub-division of the volcanic succession into distinct units. A lapilli metatuff unit hosts the base metal and precious metal mineralisation. The sulphides are best developed in the upper part of this unit, together with intercalated barite-rich horizons and cherts. A series of structural events have modified the attitude of the lithological units and disrupted the continuity of the orebody. The orebody comprises stratabound lenses of massive to semi-massive and often banded sulphides, as well as disseminated sulphide mineralisation. The dominant base metal mineralogy consists of pyrite, sphalerite, chalcopyrite, galena and tennantite. Native silver and various copper-silver sulphides are also associated with the base metal sulphides. A vertical zonation of the mineralisation exists, from pyrite-chalcopyrite-rich ore in the footwall, to pyrite - chalcopyrite-sphalerite-galena-barite-rich ore towards the hanging wall. Geochemical studies indicate that the Bien Venue lithologies are rhyolitic to rhyodacitic in composition and show a calc-alkaline affinity. The mobility of some elements at Bien Venue has been clearly demonstrated. This is believed to be associated with hydrothermal alteration that has led to SiO2 and MgO enrichment, as well as K2O depletion, in the wall rocks of the deposit. The geological setting and nature of the mineralisation at Bien Venue suggest that it is an example of a volcanogenic exhalative sulphide deposit. In terms of the classification scheme suggested by Hutchinson (1973, 1980), Bien Venue would best be described as a Primitive type deposit that contains barite. / Thesis (M.Sc.)-University of Natal, 1990

Acid mine drainage (AMD) is a worldwide environmental problem associated with the mining wastes, generated from active and inactive mining sites from mineral processing activities. AMD is defined as the drainage that occurs as a result of oxidation of sulphide minerals/wastes/tailings when exposed to air and water in the presence of chemolithotrophs namely the Acidithiobacillus sp. AMD is characterised by low pH and increased acidity due to elevated heavy metals and sulphate concentration. The acid production potential was carried out for sulphide minerals such as pyrite and chalcopyrite and copper tailings sample in the absence and presence of bacteria namely Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans. Acidity was generated in all the cases due to the oxidation of the mineral samples. The oxidation was found to occur at a higher rate in the presence of the bacteria compared to the control samples. Bioremediation experiments were conducted on acid mine water collected from the Ingaldahl Mines, Chitradurga, Karnataka, India, using organic and inorganic substrates. In the experiments with rice husk, complete removal of metal ions from the acid mine water was achieved with an attendant increase in the pH of the acid mine water from 2.3 to 5.5. About 21% of sulphate could be removed using Dsm. nigrificans from acid mine water pretreated with rice husk at pH 5.5 and this was further increased to 40% by the supplementation of organic components. The rice husk filtrate was found to serve as a good growth medium for Dsm. nigrificans. About 96 % of Fe, 75 % of Zn, 92 % of Cu and 41 % of sulphate removal was achieved from the acid mine water of pH 2.4 with a concomitant increase in the pH value by two units after interaction with the tree bark. About 56 % and 71 % of sulphate reduction could be achieved at initial pH values of 4.1 and 5.5 respectively of the acid mine water pretreated with E. tereticornis (Sm) bark, after inoculation with Dsm. nigrificans. The complete removal of Fe2+ and Fe3+, 80% of Zn, 83% of Cu and 62% of sulphate could be removed from acid mine water using fly ash as the substrate with an increase in pH of acid mine water from 2.3 to 7. About 68% of sulphate reduction at pH 6.8 could be achieved in acid mine water pretreated with fly ash in the presence of Dsm. nigrificans. With red mud as the substrate, complete removal of all the metal ions namely Fe2+, Fe3+, Zn, and Cu from acid mine water was achieved with a concomitant increase in the pH from 2.3 to 8. The sulphate reduction was increased to about 51% at pH 7.2 when the acid mine water pretreated with red mud was inoculated with Dsm. nigrificans. The adsorption experiments carried out on the acid mine water using either organic or inorganic substrates indicated that the free energy of adsorption was negative for all the chosen metal ions attesting to favorable interaction. The adsorption isotherms of the metal ions for rice husk exhibited Langmuirian behaviour, while those for the other substrates adhered to both Langmuir and Freundlich relationships. The adsorption process was found to be endothermic in nature for rice husk, fly ash and red mud. On the contrary, the adsorption onto tree bark showed exothermic behaviour. The adsorption kinetics of the metal ions onto the various substrates adhered to the first order Lagergren equation. The metal uptake processes by the organic and inorganic substrates chosen for this study involve ionic, chemical and physical forces of adsorption. The different types of functional groups present on the surface of the substrates such as carboxyl, hydroxyl and carbonyl, as revealed by FTIR spectroscopic studies, partake in metal binding. The metal ions will also be adsorbed by complexing with the negatively charged reaction sites on the substrate surfaces. Furthermore, the complex solution chemistry of the metals as a function of pH has also to be taken into consideration. The mechanism of sulphate reduction by Dsm. nigrificans in the presence of organic carbon can be illustrated as: 2CH2O + SO42- + 2H+  2CO2 + 2H2O + H2S M2 + H2S  MS  + 2H+ where, CH2O represents the organic matter and M represents the metal ion.

SP, resistivity/IP and seismic refraction responses of the Woodlawn Orebody and Mt.Bulga Deposit are examined and compared. Both exhibit similar responses produced mainly by uneconomic and disseminated sulphide mineralization and host rock features, demonstrating that the magnitude and character of electrical and seismic responses are not reliable indicators of size and economic sulphide content of volcanogenic sulphide ores. SP, soil geochemistry and electrogeochemistry are found to be the most effective exploration methods followed by resistivity/IP and seismic refraction. The large SP responses over both ore zones are simulated using new methods which allowed the width and depth of oxidation to be computed. Conventional and compensation array resistivity responses best define the deposits. Computer simulation shows that dipole- dipole and Unipole arrays are most useful. First order IP responses are large and similar, but the ore zones are not easily distinguished from polarizable host rocks. Second order responses, at Woodlawn, better define these lithologies and cross-plots of EM coupling removed first order parameters prove useful. The supergene and gossan zones are defined as sources of electrical anomalies and correlate with interpreted SP sources. Seismic velocities of fresh Woodlawn ore samples indicate only small contrasts with host rocks. Refraction travel-time data are highly complex but host rocks are clearly distinguished by their seismic velocities. Both deposits appear as low velocity zones at the general bedrock level which are shallower and narrower than the electrical sources associated with the ore zones. Extensive model simulation shows that the Reciprocal interpretation method is most useful when compared to other time- term methods for refraction interpretation but has some limitations. Computer simulation shows the significance of non- critical refractions, diffractions and laterally hidden zones which define the lateral resolution of the refraction method. The results of this study and the interpretative techniques developed will assist the exploration for similar and deeper massive volcanogenic orebodies in comparable geological environments.

The Mount Ayliff Complex (MAC) is situated on the border between Kwa-Zulu Natal and the Eastern Cape provinces in the Republic of South Africa, approximately 90 km due west of Port Shepstone. The Complex forms part of the Karoo Igneous Province and includes five lobes (Ingeli, Insizwa, Tonti, Tabankulu, and Horseshoe) that are the remnants of a single continuous intrusive sheet that had an original extent of 18,000km2• The current outcrop is estimated at 800km2• The lobes all show extensive internal differentiation, from basal ultramafic cumulates to diorites and monzonites at the top, while most other intrusions in the Karoo Igneous Province cooled rapidly enough to produce relatively homogenous dolerites. Most work conducted on the Complex thus far has centered on the Insizwa lobe due to the presence of a Ni-sulphide occurrence near the base of the lobe at Waterfall Gorge. The setting of the ores has analogies to the Noril'sk-Talnakh deposits, which has raised considerable exploration interest on the Mount Ayliff Complex over the last century. The current study investigates the Ni-Cu sulphide potential of the Ingeli and Horseshoe lobes, which have been poorly studied in the past. To this effect, a stream sediment survey was conducted around the Ingeli lobe to try and detect potentially hidden magmatic sulphide ores. Further, the five lobes of the Complex have been compared in terms of lithology and lithogeochemistry. Analytical techniques used for the current study include: XRF, ICP-MS and electron microprobe. Stream sediment samples were analysed using XRF and ICP-OES. Olivines from the ultramafic cumulates of the Ingeli and Insizwa lobes are undepleted in Ni, whereas olivines from the Horseshoe and Tabankulu lobes are strongly depleted in Ni. This suggests that the rocks of the latter two lobes crystallized from parental magmas that interacted with a sulphide liquid and that the magmatic flow direction was from the north to the south. The data indicate that the ultramafic rocks of the Complex plot on or near control lines between olivine and Karoo dolerite indicating that the rocks are mixtures of cumulus olivine and trapped melt of Karoo dolerite composition. There appears to be a copper enrichment towards the top of the ultramafic package in the Ingeli lobe. This pattern corresponds to other studies conducted in the InsiZWa lobe and suggests that the two lobes had originally been connected. The lowermost cumulates of the Ingeli lobe contain an enhanced crustal component suggesting some in situ contamination. No significant sulphide enrichments were encountered in the Basal Zone rocks of the Ingeli lobe. However, the stream sediment data indicate localized PGE enrichment indicating the possible presence of a localized hidden sulphide occurrence of the type found at Waterfall Gorge. Small amounts of sulphides were found associated with the Basal Zone rocks in the Horseshoe lobe consistent with the trends of Ni-depletion of olivines. However, a lack of Co depletion in the ultramafic rocks of this lobe suggests that any sulphide segregation event that did take place was of a relatively small scale. / Dissertation (MSc)--University of Pretoria, 2006. / Geology / MSc / Unrestricted

Ekobacken, Värmdö kommun, har problem med surt yt- och grundvatten med höga metallhalter. Uppmärksamheten har riktats mot berggrunden som krossats och lagrats i deponihögar. Bildningen av sur lak styrs av flertalet geokemiska egenskaper, bland annat vilka sulfidmineral som förekommer och deras kristallstruktur. Prover från Ekobacken har undersökts utifrån sulfidhalt, kristallarea för opaka mineral och surgörande potential för att kunna utröna om ett samband finns mellan kristallareafördelning och lakningsegenskaper. Proverna har mikroskopiskt undersökts i reflekterande ljus för att skilja ur vilka opaka faser som förekommer samt har tunnslip fotograferats för att bildanalysera de opaka faserna utifrån area och form. Ett statiskt laktest utfördes på proverna för att kvantifiera dess lakningsegenskaper. Resultatet visar att bergarterna bestod i stor del av kvarts, fältspat och biotit i olika fördelningar. Opaka faser som förekom var pyrit, grafit, kopparkis och magnetit. Bergarterna visade sig generellt ha hög sulfidhalt från ABA resultatet, där ett prov hade en halt på 0,61 vikt%, medan andra prov hade relativt hög bufferförmåga och därför ingen surgörande potential. Proverna som undersöktes visade sig vara likartade varandra i förhållande till kristallareafördelning av opaka faser och form. I den här studien gick ingen direkt korrelation mellan provens kristallareafördelning för opaka faser och lakningspotential att utröna / Ekobacken, Värmdö municipality, have a problem with acidic surface- and groundwater with high metal content. The attention has been directed towards the bedrock which have been crushed and stored in landfills. The production of acid drainage is controlled by multiple geochemical properties inter alia which sulphide minerals are present and the structure of crystals. Samples from Ekobacken has been collected and analysed for sulphide content, crystal-area of sulphide minerals and acidic potential to investigate if there is a correlation between crystal-area distribution and leachability. The samples were examined under reflective light microscopy to determine the different opaque phases present and the thin sections were photographed for a photo analysis regarding crystal area and shape. A static leachability test was performed to be able to quantify the samples potential to produce acidic drainage. The results show that the samples contained mostly quartz, feldspars and biotite. Opaque phases present were pyrite, graphite, chalcopyrite and magnetite. ABA results showed high sulphide content, where one sample reached 0,61 wt. % sulphide content. Other samples contained relative high ability to buffer acidic reaction and thus showed no potential to produce acidic drainage. The samples were homogenous to each other with regard of crystal-area distribution of opaque phases and aspect-ratio of individual crystals and in this study no direct correlation between the sample’s crystal-area distribution of opaque phases and potential to produce acidic drainage was apparent.

The Nebo-Babel Ni-Cu-platinum-group element (PGE) magmatic sulphide deposit, a world-class ore body, is hosted in low-MgO, tube-like (chonolithic) gabbronorite intrusion in the West Musgrave Block, Western Australia. The Nebo-Babel deposit is the first significant discovery of a nickel sulphide deposit associated with the ca. 1078 Ma Giles Complex, which is part of the Warakurna large igneous province (LIP), now making the Musgrave Block a prime target for nickel sulphide exploration. The Musgrave Block is a Mesoproterozoic, east-west trending, orogenic belt in central Australia consisting of amphibolite and granulite facies basement gneisses with predominantly igneous protoliths. The basement lithologies have been intruded by mafic-ultramafic and felsic rocks; multiply deformed and metamorphosed between 1600 Ma and 500 Ma. The Giles Complex, which is part of the Warakurna LIP, was emplaced at ca. 1078 Ma and consists of a suite of layered mafic-ultramafic intrusions, mafic and felsic dykes and temporally associated volcanic rocks and granites. The Giles Complex intrusions are interpreted to have crystallised at crustal depths between 15km and 30km and are generally undeformed and unmetamorphosed.

Attractive particle interactions which lead to the hetero-aggregation or 'sliming' of silicate clay gangue and valuable sulphide mineral particles are encountered in a number of hydrometallurgical and flotation processes. Sliming leads to poor recovery of the valuable minerals and high recovery of the clay gangue minerals in flotation concentrates. In the present work, the hetero-aggregation mechanism of hydrophilic mica clay mineral sericite (or muscovite) and hydrophobic chalcocite was investigated by probing the particle interactions and the prevailing interfacial chemistry under dispersion conditions where the individual chalcocite and sericite particles displayed negative zeta potentials. The mitigation/suppression of the hetero-aggregation was examined via the prudent control of dispersion conditions and pulp chemistry (i.e., pH modification and solution speciation control) and the use of two, anionic, polymeric dispersants with different molecular weight and functionality (carboxylate-substituted polyacrylamide, Cyquest 3223 and sulphonate-substituted polymaleic acid, P80 co-polymers) as dispersants. The adsorption behaviour of both polymers onto both minerals under industrially relevant suspension conditions have been quantified in terms of the polymer adsorption density and the adsorbed layer characteristics. These interfacial layer properties which impact on the mineral particles' zeta potentials and interactions, and also underpin the dispersion efficacy of polymers were characterized, using interfacial and solution analytical methods and TM-AFM imaging analysis.

[Truncated abstract] As mineral deposits continue to be mined, the non economic gangue materials such as sulphides (e.g. pyrite) that are extracted as part of the ore body or overburden are deposited within the waste rock and/or milled tailings. As a result of natural weathering processes, these reactive materials represent a potential hazard to surrounding environments. A major consequence, resulting from mine-waste impoundments containing sulphidic materials, relates to the offsite movement of low pH leachates containing elevated concentrations of metal ions posing a contamination threat. The processes and mechanisms acting in the formation of acid mine drainage (AMD) are highly variable and, to a high extent, controlled by climatic conditions as the main driver of water flow and wetness of the system which in turn determines the availability of oxygen as well as water for pyrite weathering. In particular, this thesis is based on the hypothesis that in semiarid and arid climates the acid production may be water … The experiments were repeated at different water contents ranging from 0.24 to 0.33 cm3 cm-3. Breakthrough curves (BTC) of Li+, K+, Ca2+, Mg2+, Na+ and pH were measured and described with models of different complexities. This included the use of a simple linear and non-linear isotherms for Li+ alone, a binary Li+ - K+ ion exchange, and a complete multicomponent chemical equilibrium description of ion transport. The latter, by including dissolution of primary minerals which released base cations such as Mg2+, Ca2+ and K+ explained some of the elution patterns of base cations for which the Li+ - K+ exchange was the dominant process. Furthermore, under unsaturated water flow conditions, retardation of Li+ increased with decreasing water content. Thus solute mobility in mafic rock tailings appears to decrease under strongly unsaturated water flow conditions.