The Stillwater Complex J-M reef, the only economic platinum deposit in the United States, consists of a 0.5 to 4 m-thick stratiform horizon of PGE-rich sulfides in an Archean layered mafic intrusion. The origin of this reef has been studied extensively using geochemical methods, yet remains highly debated. Dynamic magmatic processes have been virtually ignored in these geochemical studies. Magnetic methods provide a proven inexpensive approach to offer rapid, and reproducible results to deliver insight into these dynamic processes. I propose to investigate the variations of magnetic properties of layered rocks of the Stillwater Complex in the stratigraphic vicinity of the J-M reef. In this study, detailed magnetic methods were performed on a 115 ft core containing the J-M reef and adjacent rocks. A previously undiscovered cyclicity of magnetic susceptibility was found in the hanging wall and J-M reef section. Further tests were performed to determine the origin of the magnetic cycles. The footwall section lacked the magnetic properties seen in the J-M reef and hanging wall rocks. Both anisotropy of magnetic susceptibility, and high field magnetic data was collected at a high resolution interval along the core. It is possible that the results of this study can be used to constrain the origin of the ore body.

>Magister Scientiae - MSc / The Platreef, is a contact-type pyroxenitic reef in the Northern Limb of the Bushveld Complex, enriched in platinum group elements (PGE) and base metal sulfides (BMS). Relatively subdued mining in the Platreef, compared to RLS, has been attributed to limited knowledge regarding irregular distribution, complex style and genesis of PGE mineralisation in the Platreef. This study was, therefore, aimed at investigating the petrogenesis of the Platreef, particularly to evaluate whether the formation of the ore reefs resulted from a single or multiple sill-like magma intrusions. The study also sought to unveil the interplay of fractional crystallisation, hydrothermal fluid activities, floor rock and crustal contamination on the formation of Platreef types, PGE mineralisation and the magma source.

Masters of Science / The redistribution patterns of trace elements related to ore mineralisation in the secondary environment are the foundation of regolith exploration geochemistry. Understanding the controls of these element patterns is important for the detection of underlying ore deposits, especially in areas where bedrock is concealed by extensive regolith. The study area, which hosts PGE and gold deposits within the Stella Layered Intrusion is one such area. A major aim of this study was to use major element data to characterise the regolith materials enclosing the PGE mineralisation in the Stella Layered Intrusion to ascertain the degree of weathering that has occurred. Furthermore, the study aimed to relate the weathering patterns in regolith to the distribution of pathfinder elements of PGEs and gold in areas proximal and distal to the mineralised zones. The study was conducted using XRF data, which included major oxide and trace element data. These data were used to characterise regolith materials (scatter plots, K/Al versus Mg/Al plots) and calculating indices that determine the degree of weathering such as CIA and ICV indices as well as A-CN-K and A-CN-FM diagrams. Signatures of pathfinder/ trace elements were enhanced by hydroxylamine hydrochloride partial selective leach technique. The distribution patterns of the partial leach data were compared to the intensity of weathering and weathering products, e.g. manganese oxides, carbonates in areas proximal and distal to the ore zone. In the Serpens North Prospect, the major horizons that were identified include saprolith, stone line and aeolian sands. Incipient calcrete formation occurs in some parts of the Sirius Prospect, while in some parts, well developed, thick calcrete layers are found interlayered with the saprolith and aeolian sand.

>Magister Scientiae - MSc / This work reports the use of a pencil graphite electrode (PGE) as inexpensive and sensitive electrochemical sensing platform fabricated by using electrochemically reduced graphene oxide (ERGO) in conjunction with an in-situ plated thin mercury film. For the first time the ERGOHgF-PGE sensor is proposed for simultaneous detection of cadmium (Cd2+), copper (Cu2+), lead (Pb2+) and zinc (Zn2+) using N-Nitroso-N-phenylhydroxylamine (cupferron) as complexing agent by square-wave adsorptive cathodic stripping voltammetry (SW-AdCSV). The technique is based on the adsorption of cupferron- metal ion complexes onto the surface of the ERGO-HgFPGE at 0.1 V for 60 s carried out in 0.1 M acetate buffer solution (pH 4.6). The synthesized graphene oxide (GO) and graphene nanosheets (GNs) were characterized using different analytical techniques such as FT-IR which confirms the presence of oxygen moieties embedded in the graphitic structure and further demonstrated by UV-Vis, validating the synthesis of GO / 2023

Armored scale insects (Hemiptera: Diaspididae) are among the most invasive insects in the world. They have unusual genetic systems, including diverse types of paternal genome elimination (PGE) and parthenogenesis. Intimate relationships with their host plants and bacterial endosymbionts make them potentially important subjects for the study of co- evolution. Also, in some groups, the adult female never sheds the second instars cuticle, and remains within its confines, a habit referred to as the pupillarial habit. Here we expand upon recent phylogenetic work (Morse and Normark 2006) by analyzing a partitioned dataset including armored scale and endoysmbiont DNA from one hundred and twenty three species of armored scales, represented by two hundred and fifty-four samples. Included were fragments of the nuclear protein-coding gene Elongation Factor 1α (EF1α), the D2 and D3 expansion segments of the large subunit ribosomal RNA gene 28S, and a region of mitochondrial DNA encompassing the 3' portion of cytochrome oxidase I (COI), and the 5' portion of cytochrome oxidase II (COII). Ribosomal 16S from the primary bacterial endosymbiont Uzinura diaspidicola was amplified as well. Two versions of our dataset were analyzed due to concerns over the possible effects of missing data. The first version (the full dataset) contained all 254 taxa, with every taxon having at least both the 28S and EF1α fragments. The second version (the core dataset) had only the 113 taxa for which all four fragments were available. Maximum parsimony, maximum likelihood, and Bayesian analyses were run on both versions of the dataset, as well as individually for each fragment. We find that our results were consistent across methods, and between the two versions of the dataset. It appears that including missing data had little effect on topology. Our results mirror that of the classic taxonomy, however we reconstruct a general lack of monophyly at the subfamily, tribal, and subtribal levels. Within the two major subfamilies, we reconstruct that the same developmental pathway has evolved independently. We reconstruct independent replacements of the pupillarial habit with the scale cover, followed by independent origins of early PGE. In each case there appears to be increased diversity in clades associated with the scale cover and early PGE. In light of this apparent increase we propose a new adaptive scenario under which early PGE may have evolved – the removal of male-killing paternal chromosomes. We also reconstruct the ancestor to the armored scales to Australasian in origins, and to have an ancestral diet breath that includes members of the Rosids and/or Monocot plant groups.

Ni-laterites have the potential to become unconventional ore deposits for platinum group elements (PGE). This study was conducted to determine enrichment trends of PGE as a result of the Ni-laterization process. 6 samples were selected by mine workers from the protolith, saprolite, and limonite horizons of the Ni-laterite profile from the Acoje ophiolite block, Luzon, Philippines, and sent to Luleå University of Technology (LTU). 2 samples representing the protolith are described as dunite having undergone serpentinization, 1 sample is a massive chromitite from the saprolite layer of the laterite profile, 1 sample is a massive chromitite from the limonite layer of the laterite profile, and 2 samples are limonitic soils. Total PGE contents of the investigated Acoje samples range from 161-1180 ppb with the highest contents of PGE occurring in the limonite hosted chromitite, and the lowest contents in the saprolite hosted chromitite. C1 chondrite-normalized patterns reveal distinct trends of the PGE in the different sample types: dunite samples have a positive trend from Ir-Pd, the chromitite samples have a negative trend from Ru-Pd with a negative Ir anomaly and the limonite samples have a strong positive trend from Ir-Pd. Rare earth elements (REE) chondrite-normalized patterns of the samples show a negative Ce anomaly in the limonite while the dunite and saprolite-hosted chromitite have negative Eu anomalies. Cr# (Cr/[Al+Cr]) and Mg# (Mg/[Fe2++Mg]) were analyzed using automated mineralogy and produced Cr# values ranging from 0.67 – 0.77 and Mg# values from 0.46 – 0.59.  17 platinum group minerals (PGM) were identified from the Acoje samples: 9 from the dunite, 1 from the saprolite-hosted chromitite, 6 from the limonite-hosted chromitite and 1 from the limonite. Laurite ((Ru,Os)S2) was identified in samples A-02 and A-07 and is the only primary mineral identified. Secondary PGM, thought to have formed due to alteration processes during serpentinization, were identified as alloys composed of: Cu-Pd, Cu-Pt, Pt-Ni-Cu, Pt-Fe, Ir-Ni-(Pt,Fe), and Cu-Pt-Au-(Pd-Ag). PGM are small, measuring consistently <10 µm in diameter. Laurite occurs as inclusions in unfractured chromite. PGM alloys in the dunite samples occur along the boundary of sulfide minerals or within serpentine. PGM identified in the limonite-hosted chromitite occur along interstitial fractures within chromitite or in a Fe-Al oxide matrix within pore spaces.

Thesis (MSc)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: It is widely accepted that sulphide is the carrier and concentrator of PGEs during magmatic mineralization episodes in the Merensky Reef (MR). PGE concentration peaks and sulphide volume percent peaks are very closely correlated. Koegelenberg, (2011), showed in an experimental investigation that sulphide movement through a cumulate silicate and cumulate oxide pile behave in such a way that sulphide melt gets trapped in chromitite layers. When looking at the compositional distribution of sulphide within the MR it is noted that not only does the sulphide volume percent varies with MR stratigraphy but also the sulphide composition. Sulphide composition is more Cu-rich in the chromitite layers and more Fe and Ni dominated in the hanging wall to the chromitite layers. Until now the more Cu-rich assemblage of the chromitite layers are accepted to be of a sulphide melt composition compared to the Fe and Ni dominated Monosulphide Solid Solution or MSS composition in the hanging wall. In this study we used an experimental approach with a sulphide starting composition thought to exist as the parental sulphide composition of the MR to investigate the phase relations with changing temperature. It is found that the sulphide composition in the chromitite layers represent a sulphide melt composition at 1000 ± 50ºC. At 1000ºC, 50% of the sulphide system would exist as a melt. This Cu-rich melt would have segregated from the MSS and be trapped in the chromitite layer. Also at 1000ºC the partitioning of the Pt would have induced a secondary enrichment step of the Pt concentration in melt through the partitioning of Pt between a sulphide melt and a sulphide solid phase. The experimental evidence in this study points towards a possible source for the parental sulphide magma to the MR, which could have been a slightly Cu enriched mantle sulphide composition. Also, the secondary enrichment of Pt through sulphide melt fractionation at 1000ºC plays an important role in the shaping of the ore body. / AFRIKAANSE OPSOMMING: Dit word wydliks aanvaar dat die sulfied fraksie van die Merensky Rif (MR) die draer en die konsentrasie agent is vir Platinum Groep Elemente (PGE`s) gedurende mineralisasie episodes. PGE konsentrasie en sulfied volume persentasie is op `n hoogtepunt by gelyke stratigrafiese posisies in the MR. Koegelenberg, (2011), het deur middel van eksperimente bewys dat `n sulfied smelt deur `n voorafbestaande kumulaat laag kan beweeg en dat veranderende fisiese eienskappe tussen sulfied smelt en silikaat kristal en sulfied smelt en chromiet kristal, die sulfied smelt sal opsuig en verhoud om verder deur te suipel. Dit is egter oplettend dat nie net die sulfied volume persentasie varieer as `n funksie van die MR stratigrafie nie, maar ook die sulfied samestelling. Die meer Cu-ryke sulfied samestelling in die chromiet lae word aanvaar as `n sulfied smelt fraksie en die meer Fe en Ni dominerende sulfied samestelling in die oorhangende wandgesteentes verteenwoordig die Monosulfied Vaste Oplossing (MVO) soliede fase. In hierdie studie maak ons gebruik van eksperimentele petrologie tesame met `n begin samestelling verteenwoordigend van die oorsprong sulfied samestelling van die MR, om die fase verwantskappe van hierdie spesifieke samestelling te ondersoek. Dit word gevind dat die fraksionering tydens die vorming van die MR plaasgevind het by ongeveer 1000 ±50 C. By hierdie temperatuur is 50% van die sisteem teenwoordig as `n smelt fase. Hierdie Cu-verykte smelt was daartoe instaat om deur die silikaat laag te suipel, geskei te raak van die Fe en Ni dominerende MVO en vasgevang te word in die chromiet lae. Hierdie fraksionering van die sulfied smelt het ook `n sekondêre effek gehad op die verspreiding van Pt tussen sulfied smelt en sulfied soliede fases. Hierdie eksperimentele bewyse dui eerstens op die moontlikheid van `n sulfied smelt in die MR wat sy oorsprong vanuit `n effense Cu-verykte mantel bron kan hê, en tweedens op die belangrikheid van `n sekondêre proses vir Pt re-distribusie tydens die vorming van die MR.

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.

Les éléments du groupe du platine (POE) sont représentés, par l'osmium (Os),l'iridium (Ir), le ruthénium (Ru), le rhodium (Rh), le platine (Pt) etle palladium (Pd). L'or (Au) leur est fréquemment associé à cause de ses propriétés physico-chimiques voisines. Une méthode de dosage permettant la détermination de ces éléments (à l'exception de Os) à des teneurs d'ultratraces (inférieures ou égales au mg/t) a été développée dans notre laboratoire. Elle consiste en une coprécipitation et concentration de ces éléments par voie humide à haute température. Elle est associée à une détermination en spectrophotométrie d'absorption atomique électrothermique. Le matériel utilisé, la méthode analytique, son domaine d'application et ses limites font l'objet du premier chapitre. L'étude de la distribution des PGE dans le manteau supérieur est actuellement peu documentée. Avant d'aborder les mécanismes de fusion partielle ou de cristallisation fractionnée, il est nécessaire de tenter de définir une typologie géochimique la plus complète possible pour les teneurs en PGE des Iherzolites à spinelle du manteau supérieur sous continental. Le second chapitre est donc consacré à l'étude de l'écaille tectonique de lherzolites à spinelles de l'étang de Lherz (Ariège, France). La distribution des PGE dans ce complexe ultrabasique est caractérisée par une très faible pente des spectres de teneurs normalisées au manteau. Ils sont cependant fortement déprimés en Pt (< 0,5 ppb). Ce caractère a également été observé au cours d'autres analyses effectuées sur des Iherzolites à spinelle (Massif du Lubéron, Massif Central ... ) qui militent en faveur d'une généralisation de ce caractère. Les harzburgites associées aux lherzolites à spinelle de l'étang de Lherz ont permis d'aborder les phénomènes de fusion partielle et de contrôler la plus ou moins grande mobilisation des PGE par ces mécanismes. Les filons de pyroxénolites anhydre ou à amphibole ont permis par contre une approche du fractionnement magmatique dans un système ouvert: ils constituent en effet des conduits nourriciers indépendants recoupant la Iherzolite encaissante. Le comportement des PGE pendant le fractionnement d'un liquide silicaté est un phénomène complexe contrôlé par les coefflcients de partage, les paramètres thermodynamiques, la capacité en soufre du magma ... Le Filon Robert (Bande de Cape Smith, Québec, Canada) représente un liquide de type basalte komatiitique fractionné dans un système fermé. Son étude détaillée, à partir de l'évolution des teneurs calculées du liquide résiduel en équilibre avec les ségrégats fractionnés, nous a permis de caractériser plusieurs tendances au cours du fractionnement des PGE. Il est ainsi possible de mettre en évidence une précipitation des PGE contrôlée par les paramètres thermodynamiques, en étroite relation avec les caractéristiques des phases cristallisées. Cette analyse montre la complexité des mécanismes de fractionnement des PGE et souligne la non-représentativité d'une étude ne faisant intervenir qu'un seul processus de fractionnement dans ce contexte (normalisation à 100% de sulfures, diagrammes binaires de corrélation ... ). Elle montre également que dans les amas minéralisés ce ne seront pas forcement les niveaux les plus riches en sulfures qui possèderont les plus fortes teneurs en PGE.

The Marathon PGM-Cu deposit is hosted by the Coldwell alkaline complex, which consists predominantly of gabbro and syenite and was emplaced at 1108 Ma as part of the Mid-Continent Rift System. Mineralization at the Marathon PGM-Cu deposit is hosted by the Two Duck Lake Gabbro (TDLG), a fresh olivine-bearing gabbro. The Marathon deposit contains several zones of mineralization including the Basal Zone, the Main Zone and the W-Horizon. The W-Horizon is a high-grade PGE zone characterized by low S, low Cu/Pd and high Cu/Ni. The sulphide mineral assemblage is predominantly chalcopyrite and bornite. This contrasts with the Main Zone where the dominant sulphide mineral assemblage is chalcopyrite and pyrrhotite. The Main Zone contains higher S, higher Cu/Pd and shows a decrease in Cu/Pd and pyrrhotite/chalcopyrite from base to top. Four drill holes were selected for detailed analysis to characterize the W-Horizon style of mineralization. Detailed petrographic study of the pristine and largely unaltered TDLG shows that wide spread hydrothermal alteration is not responsible for the mineralization. Detailed outcrop mapping shows that the TDLG intruded as a series of multiple intrusions in a dynamic magmatic system. Geochemical studies through the W-Horizon show that the mineralization is not the result of crystallization in a layered intrusion. The results of geochemical assays and electron microprobe analysis of olivine grains show that the chemistry through the TDLG hosting the W-Horizon is erratic. This data supports the TDLG intruding as a series of sills in a dynamic conduit environment. The calculated sulphide metal tenors for the W-Horizon are higher than can be explained by closed system R Factor models. Multistage dissolution upgrading in an open system is examined as the process forming the W-Horizon. This model is able to produce the sulphide metal tenors observed in the W-Horizon. Sulphur loss also affects grades and tenors and was examined through geochemical and petrological data. The change in sulphide mineral assemblage from a pyrrhotite and chalcopyrite (S-rich) to chalcopyrite and bornite (S-poor) supports S-loss. Whole rock S and Se contents are also analyzed to investigate S loss, a lower S/Se indicates that sulphur has been removed from the system. Average S/Se values are ~800 for the W-Horizon, ~1980 for the Main Zone and ~1700 in unmineralized samples. The very low S/Se observed within the W-Horizon supports S-loss. Sulphur loss in a dynamic magmatic conduit system is proposed for the formation of the W-Horizon mineralization. In this model sulphur undersaturated basaltic magma interacted with an immiscible sulphide liquid in a magma conduit, resulting in the dissolution of sulphide into the basaltic melt and PGE enrichment.