Thesis (MScEng)--University of Stellenbosch, 2006. / ENGLISH ABSTRACT: Behaviour of palladium, platinum, copper, chloride anions, hydrogen cations, the l3-hydroxyoxime LIX 84-1 and the primary amine Primene JM-T during the extraction of Pd at the Anglo Platinum Precious Metals Refinery (PMR). The extractions of Pd, Pt and Cu into the organic phase were modelled as first-order reactions, with respect to the concentration of Pd, Pt and Cu in the aqueous phase, respectively. The movement of all other species are based on the stoichiometry of the three extraction reactions. Parameters found from literature and from previous experimental work by Johnson Matthey Technology Centre and Anglo Research (previously the Anglo Platinum Research Centre) generally describe the thermodynamic and kinetic behaviour of Pd extraction. Parameters for Pt and Cu co-extraction have been hypothesised and need to be confirmed through adequate experimental testwork. The model is fully functional and, upon completion of the simulation, all species' concentration profiles are produced. Eight mixers have been modelled as two continuous stirred tank reactors (CSTRs) with counter-current flow, and the concentration profiles are given as functions of the residence time of the two CSTRs. A secondary model has been created to facilitate future validation of the model by mimicking the movement of species in titanium unit cell batch extraction experiments. Both the primary and secondary models are based on identical thermodynamic and kinetic parameters for all reactions involved. Due to the fact that possibly inaccurate parameters were used in the construction of the Pd extraction model, the outputs shown serve to illustrate the value of the simulation model once all unknown parameters have been quantified through adequate experimental work. Keywords: Anglo Platinum, PMR, solvent extraction, kinetics, simulation. / AFRIKAANSE OPSOMMING: Model is met behulp van Matlab en Simulink ontwikkel om die beweging van palladium, platinum, koper, chloried- en waterstofione, die hidroksie-oksiem LIX 84-1 en die primere amien Primene JM-T tydens die ekstraksie van Pd by die Anglo Piatinum Precious Metals Refinery (PMR) te simuleer. Die ekstraksie van Pd, Pt and Cu na die organiese fase is gemodelleer as eerste-orde reaksies, met betrekking tot die konsentrasie van Pd, Pt en Cu in die water-fase, respektiewelik. Die beweging van alle ander chemiese spesies is gebaseer op die stoichiometrie van die drie ekstraksiereaksies. Parameters gevind uit literatuur en vanaf vorige eksperimentele werk, gedoen deur Johnson Matthey Tegnologiesentrum en Anglo Research (voorheen die Anglo Platinum Navorsingsentrum), beskryf die termodinamiese en kinetiese gedrag van elemente betrokke in Pd ekstraksie. Parameters vir pt en Cu ko-ekstraksie is aangeneem en hierdie waardes moet deur die nodige eksperimentele toetswerk bepaal word, alvorens dit in die model ingesluit word. Die model is ten volle funksioneel en, met die voltooiing van simulasies, word alle spesies se konsentrasies in die organiese en water-fase vertoon. Agt mengers is gemodelleer as twee kontinue gemengde-tenk reaktore waardeur die twee fases in teenoorgestelde rigtings vloei, en die konsentrasieprofiele van al die spesies word as funksies van die mengsel-verblyftyd in die twee reaktore gegee. 'n Sekondere model is ontwikkel om toekomstige validasie van die primere model te bewerkstellig. Waar die primere gebaseer is op die vloei-uitleg van die Pd ekstraksie-baan by PMR, is die sekondere model gebaseer op die toepaslike kondisies in toetswerk wat algemeen gedoen word in 'n titanium eenheids-ekstraksiesel. Beide die primere en sekondere modelle gebruik identiese termodinamiese en kinetiese parameters vir alle betrokke ekstraksiereaksies. Omdat moontlike onakkurate parameters in die simulasiemodel gebruik word, wys die uitsette van die model slegs die funksionaliteit wat die simulasie-model sal he sodra alle parameters deur die nodige eksperimentele toetswerk bepaal is. Sleutelwoorde: Anglo Platinum, PMR, ekstraksie, kinetika, simulasie.

M.Sc. / Please refer to full text to view abstract

A thesis submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, in fulfillment of the requirements for the degree of Doctor of Philosophy, Johannesburg, August 2017 / Titanium aluminides Ti3Al (α2), γ-TiAl and TiAl3 have received much attention for potential applications where light weight for energy saving, room temperature corrosion resistance in aqueous solutions, high-temperature oxidation resistance, or where combinations of the above are needed. Gamma-TiAl of composition Ti-47.5 at.% Al with additions of platinum group metals (PGMs: Pt, Pd, Ru and Ir) was investigated for microstructure, hardness, room temperature aqueous corrosion, high-temperature oxidation resistance, mechanical alloying and consolidation by spark plasma sintering, and coating on titanium Grade 2 and Ti-6Al-4V substrates. Gamma-TiAl of Ti-47.5 at.% Al produced by melting and casting gave a microstructure consisting of γ grains and lamellar grains with alternating of α2 and γ phase lamellae. Additions of 0.2, 1.0, 1.5, and 2.0 at.% PGMs introduced new phases of high PGM contents. The γ and lamellar phases were still present. The additions of PGMs significantly improved the aqueous corrosion properties at room temperature, by improving the pitting corrosion resistance of the γ-TiAl alloy by modifying its hydrogen evolution of the cathodic reaction. The presence of PGMs also influenced the oxidation behaviour of γ-TiAl at 950°by forming the Z-phase which stabilized a continuous protective Al2O3 phase. However, Ti-47.5 at.% Al, being a two-phase alloy (α2+γ), PGMs could not sustain a stable Z-phase, as it transformed into an oxygen supersaturated Ti3Al, which subsequently led to the formation of TiO2+Al2O3, a non-protective oxide mixture. The optimal PGM addition to γ-TiAl was 0.5 at.%, with iridium giving the best room temperature corrosion and high-temperature oxidation resistance. Mechanical alloying of Ti and Al pure powders with PGM additions gave powders where α2 and γ were only identified after heat treatment. Consolidation of the mechanically alloyed powders by spark plasma sintering gave different microstructures from the cast alloys, with continuous α2 and γ phases and evenly distributed nanometer-sized alumina, and much higher hardnesses. Cold spraying the mechanically alloyed powders on to titanium Grade 2 and Ti-6Al-4V substrates gave coatings of irregular thickness, dense near the substrates with porosity at the top, giving poor oxidation protection. / CK2018

>Magister Scientiae - MSc / The purpose of this study was to develop a high performance-lower cost catalyst to be applied in Direct Methanol Fuel Cells (DMFC). The study also aimed to prepare plurimetallic supported platinum (Pt), platinum-ruthenium (PtRu), platinum-ruthenium-vanadium (PtRuV) and platinum ruthenium-vanadium-iron (PtRuVFe) upon multi-walled carbon nanotube (MWCNT) as well as upon multiwalled carbon nanotube-titanium oxide (MWCNT/TiO2) supports. Platinum is very active but prone to poisoning by carbon monoxide (CO), which may be present in the fuel used in fuel cells. The focus on the use of methanol was because of its better reaction kinetics, and better performance in direct methanol fuel cells (DMFC) better than proton exchange membrane fuel cell (PEMFC). When Pt is alloyed with another platinum group metals (PGM) the alloying decreases the over-potential for reactions critical in the fuel cells. Proton exchange membrane fuel cell (PEMFC) performance may be improved at low metal loading, when supported pluri-metallic catalysts are applied since the trimetallic catalysts may promote high catalyst utilisation. In practice, DMFC require electrodes with a Pt loading to achieve acceptance fuel cell (FC) power performance. The aim of this study was therefore the reduction of the catalyst loading through further improvement of mass activity of Pt based catalysts by partial substitution of the noble metal/metals, and the use of a carbon support that will provide high surface area, good electrical conductivity and high stability. MWCNT supported pluri-metallic (PtRuVFe,) and bimetallic (PtRu) nanoparticles possessed characteristic of increased surface area, improved electron transfer rate, enhance electro-catalytic activity and promoted stability.

In this study, various techniques of hydrometallurgy and ultrasound-assisted solvent extraction were used to recover the platinum group metals (PGM¡¦s) from a composite sample of honeycomb-type autocatalysts. After they were removed from the converter casings, the autocatalyst substrates were first crushed and then ground by a ball mill. The recovery procedures employed are shown as follows: (1) dissolve PGM¡¦s from ground spent autocatalyst by aqua regia leaching; (2) separate PGM¡¦s from base metals in the aqua regia leachate by metal cementation using zinc powder so that PGM¡¦s can be precipitated out; (3) the PGM¡¦s precipitate was first dissolved by aqua regia, then proceed to remove nitrate and hydrochloride within. The residue was further dissolved in hydrochloride acid as a preparation step for solvent extraction; (4) the PGM¡¦s pregnant solution of hydrochloride acid was treated by solvent extraction and stripping to separate and purify each component of PGM¡¦s. Effects of ultrasound agitation on the efficiency of solvent extraction was also evaluated in this work. Results of aqua regia leaching experiments have shown that the quantity of dissolved PGM¡¦s increased as the solid-to-liquid ratio decreased. The maximum dissolved quantity of PGM¡¦s could be obtained by a 3-hr leaching time. At this stage, the PGM¡¦s recoveries are 80-90% for platinum and rhodium and greater than 99% for palladium. The result of a preliminary test has indicated that acetic acid can not effectively separate the PGM¡¦s and base metals. Thus, the method of cementation by zinc powder was employed to separate PGM¡¦s from base metals. Before cementation, the aqua regia leachate was diluted and pH-adjusted to greater than 2. In so doing, an almost complete cementation (>99%) could be obtained by the least quantity of zinc powder. In addition, the base metals occurred with the PGM¡¦s precipitate have been minimized except lead and zinc. While palladium was extracted by di-n-octyl sulfide (DOS), ultrasound assistance has rendered a complete extraction within a few minutes. At this stage, the extraction efficiency was found to be independent of the HCl concentration. It was found that platinum and rhodium were not extracted by DOS. When platinum was extracted by tri-n-octylamine (TOA) and assisted by ultrasound, rhodium will be extracted at the HCl concentration higher than 4M. Thus, TOA is not an effective chemical for selective extraction of platinum. TOA was then replaced by tributyl phosphate (TBP). Experimental results have indicated that the extraction of platinum using TBP was affected by the HCl concentration. The best result was obtained when the HCl concentration was 5M. Extraction by TBP was found to be fast. It took only 20-30 seconds to reach the equilibrium even with no ultrasound assistance. But multi-stage extractions are generally required to extract platinum completely. Rhodium was found to be not extracted by TBP. After palladium and platinum were extracted, only rhodium was remained in the reffinate. In summary, solvent extraction using DOS and TBP has made it possible to separate palladium, platinum, and rhodium effectively. In the palladium stripping solution almost no base metals was determined. However, zinc and lead were found in the platinum stripping solution and the rhodium-containing raffinate. These base metals should be removed to achieve a better purity for each precious metal. The TCLP (i.e., a leaching test for toxicity) result of the autocatalyst substrate after aqua regia leaching has found to be non-hazardous. However, several streams of wastewater and acid gas generated in the recovery process should be properly managed to avoid the secondary pollution.

Thesis (MSc.(Metallurgy)--University of Pretoria, 2008. / Includes bibliographical references.

M. Tech. Chemical Engineering. / Discusses the objectives of the research project are to: 1. Develop a cost effective technique for modifying the surface groups of ACs with a view to induce selectivity properties towards PGMs. 2. Characterize the chemically treated ACs. 3. Determine adsorption capacities and selectivity of Amine treated ACs by performing batch adsorption tests. 3. Investigate the adsorption of Pt (IV) in a Continuous stirred tank reactor. The data generated according to the project objectives will assist in obtaining the following informations. 1. Adsorption isotherms - Find the maximum adsorption capacity of ACs for different solution concentrations, and temperature. Determine the effect of base metals on adsorption and hence extend the adsorption isotherm equation from single component to a multi-component adsorption isotherm. 2. Kinetics data - Determine the rate of change of metals in solution with time at various initial concentration, temperature and acid strength. 3. Characterization of modified ACs - Determine surfaces morphology of ACs using SEM-EDS.

Στα πλαίσια της παρούσας διατριβής μελετήθηκαν οι διεργασίες κοιτασματογένεσης των χρωμιτιτικών εμφανίσεων των οφιολιθικών συμπλεγμάτων του Βούρινου και της Πίνδου, σε συνδυασμό με τη συνδεόμενη με αυτές μεταλλοφορία των στοιχείων της ομάδας του λευκόχρυσου (PGE). Ιδιαίτερη έμφαση δόθηκε επίσης στην πετρογενετική εξέλιξη των μανδυακών ενοτήτων των δύο οφιολιθικών ακολουθιών, προκειμένου να εξαχθούν γενικότερα συμπεράσματα σχετικά με την προέλευση και τη διαμόρφωση των οφιόλιθων του ΒΑ Ελλαδικού χώρου. Γεωτεκτονικά το οφιολιθικό σύμπλεγμα του Βούρινου τοποθετείται στην Υποπελαγονική ζώνη, ενώ εκείνο της Πίνδου βρίσκεται τεκτονικά επωθημένο επί του Ηωκαινικής ηλικίας φλύσχη της ομόνυμης ισοπικής ζώνης. Αμφότερα τα συμπλέγματα θεωρείται ότι αντιπροσωπεύουν υπολείμματα του ενός ενιαίου ωκεανού, τα οποία σήμερα βρίσκονται επωθημένα επί του δυτικού περιθωρίου της Πελαγονικής μικροπλάκας. Αν και εμφανίζουν έντονα χαρακτηριστικά τεκτονικής καταπόνησης και οι δύο ακολουθίες διατηρούν όλο τους τύπους πετρολογικών ενοτήτων που συνθέτουν το φάσμα ενός πλήρως ανεπτυγμένου οφιολιθικού συμπλέγματος. Όλοι οι σχηματισμοί που μελετήθηκαν στα πλαίσια της παρούσας διατριβής προέρχονται από τις μανδυακές σειρές των δύο οφιολιθικών συμπλεγμάτων. Οι μανδυακοί τεκτονίτες αποτελούν τον κύριο όγκο του συμπλέγματος του Βούρινου, ενώ οι μανδυακής προέλευσης σχηματισμοί στο οφιολιθικό σύμπλεγμα της Πίνδου συνθέτουν την επονομαζόμενη ενότητα της Δραμάλας. Στον Βούρινο η δειγματοληπτική έρευνα κάλυψε τις σημαντικότερες από κοιτασματολογικής άποψης περιοχές του βόρειου και νότιου τμήματός του, ενώ στην Πίνδο δείγματα συλλέχθηκαν από τα κεντρικά και νότια τμήματα της όλης ενότητας της Δραμάλας, καθώς και από μανδυακής προέλευσης, ευμεγέθη, εξωτικά τεμάχη εντός της ενότητας της Αβδέλλας mélange. Η υπαίθρια μελέτη των μανδυακών ενοτήτων και στα δύο συμπλέγματα οδήγησε στις ακόλουθες διαπιστώσεις: α) το βόρειο τμήμα του οφιολιθικού συμπλέγματος του Βούρινου εμφανίζει σαφώς εντονότερα χαρακτηριστικά πλαστικής παραμόρφωσης σε σχέση με το νότιο, στο οποίο επικρατούν χαρακτήρες εύθραυστης-ημιπλαστικής παραμόρφωσης. Μια ανάλογη διάκριση, ασθενέστερα ωστόσο εκπεφρασμένη, θα μπορούσε να ειπωθεί πως ισχύει και όσον αφορά στην διάρθρωση των περιοχών Μηλιάς-Πεύκης, αντίστοιχα, στην Πίνδο. β) Η στατιστική ανάλυση των κινηματικών δεικτών συμφωνεί με μια προς τα ΒΑ διεύθυνση επώθησης για τον βόρειο Βούρινο και τη Μηλιά και με μια ΝΑ διεύθυνση τοποθέτησης για τον νότιο Βούρινο και το υπερβασικό τέμαχος της Πεύκης. γ) Οι χρωμιτιτικές εμφανίσεις φιλοξενούνται από δουνίτες και συγκεκριμένα στην πλειονότητα των θέσεων που παρατηρείται η ανάπτυξη χρωμιτικής μεταλλοφορίας το συνοδό είδος περιδοτίτη είναι ο λεπτοκρυσταλλικός δουνίτης (υγιής ή σερπεντινιωμένος). Πέρα από την σε όρους κοκκομετρικού μεγέθους διαφορά του σε σχέση με τον αντίστοιχο αδροκρυσταλλικό λιθότυπο, μια επιπλέον διαφοροποίησή του από αυτόν είναι η έλλειψη φολιωμένης δομής στον πρώτο. δ) Οι χρωμιτίτες του βόρειου Βούρινου και της Μηλιάς είναι συνήθως θυλακοειδούς μορφής, ασύμφωνα-παρασύμφωνα ανεπτυγμένοι σε σχέση με τους πιο άμεσους προς αυτούς αδροκρυσταλλικούς δουνιτικούς-χαρτσβουργιτικούς περιδοτίτες, ενώ τα χρωμιτικά κοιτάσματα του νότιου Βούρινου και της Πεύκης ακολουθούν στρωματοειδή, σύμφωνη-παρασύμφωνη δομική ανάπτυξη. ε) Οι χρωμιτίτες και των δύο συμπλεγμάτων εμφανίζουν μεγάλη ποικιλία ιστολογικής ανάπτυξης, ωστόσο διαπιστώθηκε μια συστηματική διαφοροποίηση όσον αφορά στο κύριο τύπο ιστού της κάθε χρωμιτικής μεταλλοφορίας. Έτσι στους χρωμιτίτες του βόρειου Βούρινου και της Μηλιάς επικρατεί ο συμπαγής και ο ιστός τύπου λεοπαρδάλεως, ενώ στους χρωμιτίτες του νότιου Βούρινου και της Πεύκης το επικρατέστερο είδος είναι ο ιστός κατά πλάκες. στ) Στο νότιο Βούρινο και στην Πεύκη παρατηρούνται συχνά εναλλασσόμενοι χαρτσβουργιτικοί-δουνιτικοί "πάγκοι", ενδεικτικοί μιας στρωματομένης κατάστασης του υπολειμματικού τμήματος του μανδύα που εκτίθεται επί των συγκεκριμένων περιοχών. Επίσης, ο αριθμός των πυροξενιτικών (ροδινγκιτιωμένων και μη) φλεβών είναι υψηλότερος στις περιοχές αυτές σε σχέση με εκείνων του βόρειου Βούρινου και της Μηλιάς. Στην πλειονότητα των περιπτώσεων οι φλέβες διατέμνουν τα κοιτάσματα χρωμίτη, στοιχείο που υποδεικνύει ότι δεν συνδέονται γενετικά μαζί τους, με μόνη εξαίρεση μια χρωμιτική εμφάνιση που φιλοξενείται σε πυροξενιτική φλέβα στην περιοχή της Πεύκης. ζ) Πάντα κοντά στις περιοχές εμφάνισης των κοιτασμάτων η τυπική λιθολογική διαδοχή προς αυτά είναι η: ±κλινοπυροξενομιγής χαρτσβουργίτης-κανονικός χαρτσβουργίτης-μεταβατικός χαρτσβουργίτης-αδροκρυσταλλικός δουνίτης-λεπτοκρυσταλλικός δουνίτης-χρωμιτίτης. Η οποιαδήποτε απόκλιση από την γενική αυτή διαδοχή είναι σπάνια, ακόμη και σε περιπτώσεις μικρών χρωμιτικών φακών. η) Η συχνή παγίδευση χαρτσβουργιτικών τεμαχών εντός αδροκρυσταλλικών δουνιτών υποδηλώνει την προέλευση των τελευταίων από τους πρώτους, ωστόσο περιπτώσεις αντικατάστασης φολιωμένων χαρτσβουργιτών από λεπτοκρυσταλλικούς δουνίτες υποδεικνύουν ότι κάποιοι λιθότυποι δεν έχουν, όπως αναμένεται, υπολειμματική προέλευση. θ) Η παρουσία κλινοπυροξενομιγών χαρτσβουργιτών είναι πιο συστηματική στην Πίνδο, ενώ στον Βούρινο απαντώνται πιο συχνά στείροι λεπτοκρυσταλλικοί δουνίτες κυρίως υπό τη μορφή φλεβών, πάγκων ή φακών. ι) Το χρωμιτικό κοίτασμα του Κορυδαλλού φιλοξενείται μέσα σε ένα εξωτικό, δουνιτικό τέμαχος, το οποίο περιέχεται εντός της οφιολιθικής mélange της ενότητας της Αβδέλλας που αναπτύσσεται στη συγκεκριμένη περιοχή. Τέλος, η συνολική αξιολόγηση όλων των διαθέσιμων γεωλογικών, ορυκτοχημικών, πετρολογικών και κοιτασματολογικών στοιχείων, υποδηλώνει ότι οι μανδυακές ενότητες και των δύο ακολουθιών γεννήθηκαν σε ένα κέντρο ώριμης διάνοιξης (MOR) και στη συνέχεια αναδιαμορφώθηκαν ως τμήματα ενός περιθωρίου πάνω από μια ζώνη καταβύθισης (SSZ). Η μετάβαση από τον Βούρινο στη Μηλιά και την Πεύκη και εν τέλει στον Κορυδαλλό πιθανά ισοδυναμεί με τη μετάβαση από το περιβάλλον μιας λεκάνης μπροστά από νησιωτικό τόξο στο (χώρο κάτω από το) ίδιο το τόξο και τέλος σε μια μικρών διαστάσεων περιθωρειακή λεκάνη πίσω από αυτό. / In the present thesis the processes of the genesis of the chomitite occurrences of the Vourinos and Pindos ophiolite complexes combined with their content in platinum group elements are studied. Special attention is given to the petrogenetic evolution of the mantle units of both ophiolite sequences in an attempt to understand better the origin and the formation of the ophiolites of the NW Greek area. In geotectonic terms the ophiolite complex of Vourinos belongs to the Ypopelagonic isopic zone, while the Pindos ophiolites are tectonically thrusted onto the Eocenic flysch of the Pindos zone. Both complexes are considered as remnants of a certain ocean, which today are found tectonically thrusted over the west margin of the Pelagonic micro-plate. Beyond the fact that both complexes show characteristics of intense tectonic deformation, they do preserve all the types of the petrologic sequences that compose a complete ophiolite complex. All the formations that have been studied in the present thesis are coming from the mantle units of both complexes. The main part of the Vourinos ophiolite complex is composed of mantle tectonites, while the mantle formations in the Pindos ophiolite complex compose the so-called Dramala unit. In the Vourinos complex the sampling covered the most important ore hosting areas of its northern and southern part, while in the Pindos complex several samples were taken from the central-southern parts of the Dramala unit and from exotic blocks of mantle origin of the Avdella mélange unit. The field investigation in both complexes has led to the following conlusions: a) The northern part of the Vourinos ophiolite complex shows clearly more characteristics of plastic deformation compared to its southern part in which characteristics of brittle to semi-plastic deformation prevail. A similar, but not so well-expressed discrimination can be made as far as concerns the structure of the areas of Milia and Pefki in the Pindos complex. b) The statistical analysis of several motional indicators shows a NE thrust direction for the northern sector of the Vourinos complex and the area of Milia and a SE direction of motion for southern Vourinos and Pefki. c) The chromitites are hosted in dunites and in the majority of the chromitite occurrences the accompanying rock-type is thin-grained dunite (serpentinised or not). In contrast to coarse-grained dunite the thin-grained variety of dunite is not foliated. d) The chromitites of northern Vourinos and Milia are usually of podiform type, discordantly to sub-concordantly developed to their neighbouring thick-grained dunitic to harzburgitic peridotites. The chromite ores of southern Vourinos and Pefki are stratiform, having a concordant to sub-concordant structure. e) Chromitites of both complexes show a great variety of chromite textures, although in each deposit a certain type of texture predominates. In northern Vourinos and Milia the dominant textural type is massive and leopard chromitite, while in southern Vourinos and Pefki the most common texture in chromitite is schlieren. f) In southern Vourinos and Pefki are commonly observed interlayered bodies of harzburgite and dunite, which are indicative of a stratified structure of the residual mantle superimposed on these areas. The number of the pyroxenite dykes (rodingitised or not) is higher in these areas compared to those in northern Vourinos and Milia. In their vast majority these dykes cut chromitite bodies, which indicates that they are not genetically related to the ores, except for one case of a chromitite that is hosted in a pyroxenite dyke in the northern part of the area of Pefki. g) Always in the vicinity of the chromitites the lithology follows the sequence: ±Clinopyroxene-bearing harzburgite, normal harzburgite, transitional harzburgite, coarse-grained dunite, thin-grained dunite, chromitite. A different lithological transition is quite unusual. h) The common entrapment of harzburgite blocks in dunites indicates that the latter comes from the former, although replacements of foliated harzburgites from thin-grained dunite that show no mark of foliation supports the fact that some rocks may not be simply of residual origin. I) The presence of clinopyroxene-bearing harzburgites is more common in the Pindos ophiolite complex, while in the Vourinos ophiolite complex bodies of thin-grained dunite in the form of dykes, layers or lenses are more commonly observed. Finally, taking into account all the available geological, mineral chemistry and petrological data, it can be said that the mantle units of both complexes have been initially formed in a mid-ocean ridge and then have been furtherly affected by the processes that take place in the mantle wedge above a SSZ. Thus the transition from Vourinos to Milia and Pefki and then to Korydallos is obviously equivalent to the "passage" from a fore arc basin to the arc and finally to a small back arc basin.

The goal of this research was to devise a new analytical technique, using Accelerator Mass Spectrometry (AMS), to measure Platinum Group Element (PGE) concentrations to the sup-ppb levels in natural, insulating, samples. The challenges were threefold. First, a method of sputtering an insulating sample to successfully produce a stable beam of anions needed to be devised. Second, a suitable standard of known PGE concentrations had to be found and third, spectral analysis of the beam had to verify any claims of PGE abundance. The first challenge was met by employing a modified high intensity negative ion source flooded with neutral caesium that successfully sputtered insulators to produce a beam of negative ions. The second challenge, that of finding a suitable standard, was fraught with difficulties, as no synthesized standards available were found to be appropriate for this work. As a result, direction is provided for future production of standards by ion implantation. The third challenge, successful spectral analysis, was accomplished using a newly designed gas ionization detector which allowed for resolution of the interfering molecular fragment from the PGE ions. Coupled with the use of the SRIM computer programme, positive identification of all peaks in the spectra of the analyzed samples was accomplished. The success of the first and third challenges lead to the qualitative analyses of geological samples for sub-ppb levels of PGE by AMS. Quantitative analyses await only for the appropriate standards and with those will come a whole new range of research possibilities for measuring sub-ppb levels of PGE in insulating samples by AMS.

Thesis (Ph.D.)--McMaster University (Canada), 1992. / Source: Dissertation Abstracts International, Volume: 54-02, Section: B, page: 0696.