Cette étude est consacrée aux monnayages d'or frappés dans le Nord de la Gaule. Ce territoire, que Jules César nomme, le premier, "Gaule Belgique", s'étend entre la Seine et le Rhin. Les études numismatiques soulignent généralement les spécificités de cet espace, qui s'expriment particulièrement à travers l'importance de la frappe des monnaies d'or et leur typologie caractéristique. Il s'agit d'un phénomène majeur à l'échelle de la Gaule, que l'on cherche à appréhender depuis son apparition, au IIIe siècle avant notre ère, jusqu'à son terme au début de l'époque romaine.Afin de mener une réflexion sur les pratiques monétaires de cette région, nous proposons une nouvelle synthèse de l'histoire des monnaies d'or dans le Nord de la Gaule. Celle-ci passe par un réexamen des classements typologiques et des études métrologiques, ainsi que par l'élaboration de nouvelles cartes de répartition basées sur les trouvailles monétaires les plus récentes.L'approche interdisciplinaires développée dans le cadre de ce travail se traduit également par le recours aux analyses élémentaires, effectuées sur un corpus de 571 monnaies, afin d'étudier la composition de l'ensemble des émissions du Nord de la Gaule, reflets des différentes politiques monétaires et des stratégies d'approvisionnement en or au fil du temps que l'on cherche à étudier.Ainsi, l'étude typologique, métrologique et analytique des monnaies d'or du Nord de la Gaule permet d'esquisser les dynamiques monétaires mises en oeuvre au sein de cet espace. / This study deals with gold coinages struck in Northern Gaul. This territory, first referred to as "Belgic Gaul" in Caesar's writing, is located between the Seine and the Rhine. Specialists in ancient numismatics usually stress out various specific features displayed in this region, such as the unusually large amounts of gold coins which were issued there, as well as their peculiar iconography. This work investigates the implications underlying this important episode in Gaul's monetary history, from its emergence during the 3rd century BC to its end at the beginning of the Roman period.In order to enhance our knowledge about monetary uses and history in Northern Gaul, a comprehensive account is thus proposed, which combines renewed typological and metrological studies with distribution maps, based on the most recent data available at this point.Besides, our interdisciplinary approach involves elementary analysis performed on a sample of 571 gold coins. The aim is to characterize trends in the composition of all gold issues stuck in Northern Gaul, so as to identify chronological and regional patterns in monetary policies. By doing so, it thus becomes possible to stress out a distinctive set of strategies used by local authorities in order to control monetary production and to secure gold supplies through time. By combining iconographic, metrological and analytical studies, a new picture eventually emerges as regards dynamics in coin production and uses in Northern Gaul.

Shredder fines are the materials with a particle size of less than 10 mm resulting from the shredding of vehicles and complex metal scrap from industries and municipalities. This waste is currently used as landfill construction material, but Stena Recycling wanted to know whether the bottom ash from the combustion of this waste could be useful to the cement industry, and whether it would be feasible to extract Cu and Zn from this ash. To determine this the shredder fines were combusted, and the generated bottom ash underwent chemical fractionation. The leachates from this were processed using MP-AES to obtain an elemental analysis of the ash. The uncombusted shredder fines had its moisture content and calorific value determined. The shredder fines had a moisture content of approximately 11%wt. Due to the heterogeneity of the shredder fines the calorific values varied significantly across the tested samples. The average value was 7.8 MJ/kg. The chemical fractionation showed that the elements in the ash are mostly insoluble in water and ammonium acetate, as the majority remained in the solid residue. This indicates that the ash is inert, and not susceptible to heavy metal leaching. The elemental analysis showed that there is a significant amount of Fe in the ash, with reasonable amounts of Cu and Zn. This project concluded that without additional processing the ash would not be suitable for the cement industry, and that there is potential for the recovery of Cu and Zn from the ash.

This PhD. thesis is focused on application of different analytical techniques for determination of elemental composition of Moravian wine combined with analysis of selected polyphenol compounds. Two spectrometric techniques were used for elemental analysis of wine – Mass spectrometry and Optical emission spectrometry with inductively coupled plasma (ICP-MS and ICP-OES). Analysis of organic constituents of wine was evaluated by High performance liquid chromatograph with diode array detector (HPLC-DAD). Data from analysis of wine were used for construction of mathematical models for determining geographical origin of wine and for determining type of varietal wine. Data handling was performed by usage of multivariate statistical methods (cluster analysis, principal component analysis and canonical discriminant analysis). For the discrimination of wine by the geographical origin, two separate models for white and red wine were constructed. Effectiveness of discrimination of Moravian wine (with knowledge about origin) into 4 wine regions was 100 % successful for white wine and 96,43 % for red wine samples. Those models were used for cross validation test of unknown samples with result 95 % successfully classified samples of white wine and 82,15% of red wine. Besides that, mathematical model for discrimination and classification of varietal wine was made. Müller Thurgau, Riesling and Gruner Veltliner were discriminated by the usage of 8 elemental parameters. Discrimination success rate of known samples was evaluated by canonical discriminant analysis with 95,83% of correctly classified known samples and 70,83% of correctly classified unknown varietal wine (cross validation test). In addition to these part of research, impact of different grape production systems on elemental composition of wine and Vitis Vinifera was studied. The core of the study was to find the connections between the type of agriculture and chemical properties of wine and Vitis Vinifera. Two agriculture systems were assessed – Organic agriculture and Integrated pest management. . Results of this study showed that quantity and manner of pesticide application is very important factor affecting the final elemental composition of the grapevine and wine, especially the content of copper, zinc and manganese. That knowledge can be used in the future for creation of classification model of wine according to grape production system. For comparison of radical scavenging activity, electron paramagnetic resonance spectroscopy (EPR) with DPPH method was used. In the case of this study, the influence of vine growing under different farming systems on the total antioxidant activity of wine was found to be insignificant.

Knorpel ist ein kompliziertes System aus einem kollagenen Netzwerk, gefüllt mit wasserbindenden Makromolekülen (Proteoglykanen) und darin eingebetteten Zellen. Störungen in den komplexen Wechselbeziehungen können zur Gefährdung der strukturellen Integrität des Knorpels führen. Die hochauflösende Magnetresonanztomographie (NMR-Mikroskopie) kann über die Analyse der Signalintensität interne Knorpelstrukturen darstellen (hypo- und hyperintense Zonen). Mit Hilfe ionenmikroskopischer Analysemethoden (PIXE, RBS, ERDA) wurden im Knorpel (femorale und tibiale Kondyle des Hausschweins) im Querschnitt die zweidimensionalen Verteilungen der Knorpelelemente (H, C, N, O, P, S, Cl, K und Ca) aufgenommen sowie die Konzentrationen in ausgewählten Zonen bestimmt. Ergänzend wurde mit STIM die Dichteverteilung im Knorpel untersucht. Es gelang auch mit STIM, erstmalig kollagene Fasern in ihrer, bis auf den Wasserentzug natürlichen, Umgebung im Knorpel und damit unverändert in ihrer Anordnung sichtbar zu machen (keine chemische Demaskierung nötig). Die Ergebnisse wurden mit NMR- und polarisationsmikroskopischen Untersuchungen verglichen und in ihrem Zusammenhang mit den histologischen Knorpelzonen diskutiert. In den NMR-hypointensen Zonen fanden sich eine erhöhte Chlorkonzentration und punktförmige Calciumanreicherungen. Diese Zonen waren (im gefriergetrockneten Zustand) durch eine, bis zu einem Faktor vier höhere Dichte gekennzeichnet, die im maximalen Gehalt der Matrixelemente, H, C, N, O, (höchste Kollagendichte) begründet liegt. Im tibialen Knorpel konnten in der NMR-hypointensen Zone radial verlaufende einzelne Kollagenfasern nachgewiesen werden. Im femoralen Knorpel wurden in dieser Zone keine Einzelfasern nachgewiesen. Es deutete sich eine tubuläre Anordnung der Kollagenfasern an. In der hypertrophen Zone zeigten sich hohe Konzentrationen an Phosphor (Zellorganellen), Schwefel (Proteoglykane), Kalium (alkalisches Milieu) und Calcium (Vorstufe der Kalzifizierung). Die Chlorkonzentration hatte dort ihr Minimum. In dieser Zone verlaufen die Kollagenfasern radial und münden senkrecht in den Kalkknorpel. In der Tangentialfaserschicht wurde eine erhöhte Konzentration an Calcium und Phosphor beobachtet (Einlagerung von Calciumphosphaten). In dieser Zone wurden tangential verlaufende Kollagenfasern und ihr Übergang zur stärkeren Vernetzung mit teilweise arkadenförmiger Überstruktur sichtbar gemacht. Zur genaueren Aufklärung der dreidimensionalen Anordnung der Kollagenen Strukturen wurden erste Experimente zur STIM-Tomographie durchgeführt.

The present PhD is focused on the development of new analytical methods based on ICP techniques to carry out the elemental and isotopic analysis of bioethanol samples and other specimens taken along the bioethanol production process. The total sample consumption system, so-called hTISIS, has been used as sample introduction system in ICP-OES for the quantification of major and minor metals, and ICP-MS for the determination of trace metals. The hTISIS has also been successfully set up to carry out the lead isotopic analysis of bioethanol samples. Additionally, metals found in bioethanol have been monitored along the production process of this biofuel to identify the origin of these metals. Finally, volatile organic compounds have been determined in different bioethanol samples to perform the characterization of the matrices and their effect on the accuracy of the methods based on ICP techniques, developed in the present PhD for the elemental and isotopic analysis of these kind of samples. / La presente Tesis Doctoral se centra en el desarrollo de nuevos métodos de análisis basados en técnicas de ICP para llevar a cabo el análisis elemental e isotópico de muestras de bioetanol y muestras tomadas a lo largo del proceso de obtención de dicho biocombustible. Se ha empleado un sistema de consumo total de muestra, conocido como hTISIS, como sistema de introducción de muestras en ICP-OES para la cuantificación de metales mayoritarios y minoritarios, y en ICP-MS para la determinación de metales traza en bioetanol. El sistema hTISIS también se ha empleado con éxito para llevar a cabo el análisis isotópico de plomo en dichas muestras. Además, los metales encontrados en las muestras de bioetanol han sido monitorizados a lo largo del proceso de obtención del mismo para identificar el origen de dichos metales. Finalmente, se han determinado los compuestos volátiles presentes en diferentes muestras de bioetanol, con el objetivo de caracterizar las matrices y como estas pueden afectar a la exactitud de los métodos desarrollados, que emplean técnicas ICP para el análisis elemental e isotópico de este tipo de muestras.

This thesis paper examines the feasibility of using external-beam PIXE to study the surface enrichment effect in metal artifacts. By varying the energy of the incident proton beam, we penetrated the artifact's surface to different levels and were able to produce a depth profile of the elemental composition of the sample. In this study, the sample set we chose to examine consisted of ancient and modern coins. This paper first describes the surface enrichment effect and theoretically how PIXE can be used to study it. It then details the construction of the components of the external-beam setup. Many of the refinements of the hardware and experimental methods are discussed. It recounts the means of calibration of the detector and analytical tools. Finally, an accounting of the research performed on several coins is set forth, along with data showing the effectiveness of PIXE in complementing other methods of elemental analysis. We found that PIXE revealed statistically significant differences in concentrations of modern coins at the two beam energies we used. Ancient coins did not have similarly significant discrepancies between the two beam energies. The modern coin data suggested depletion in copper in copper-silver and copper-gold alloys, which is consistent with predictions of the theory of the surface enrichment effect. We suggest that the ancient coins are so deeply corroded that the PIXE beam is unable to penetrate adequately to observe surface enrichment. Comparison of our PIXE data to XRF and SEM data suggest that the trends we observed in modern coins are verified by the other methods. We therefore assert that external-beam PIXE is an effective tool for studying the surface enrichment effect, though with the beam energies available at Brigham Young University, the study must be limited to fairly modern coins.

The thesis presents an experimental investigation of combustion performance and emissions of waste cooking oil (WCO) based biodiesel. To evaluate the comparative performance of biodiesel and diesel, combustions tests were conducted using Continuous Combustion rig (CCR) and Land Rover VM diesel engine. Firstly, physical properties of WCO biodiesel and diesel samples were measured in the laboratory. Elemental analysis of WCO biodiesel showed that there are differences between the functional groups in diesel and biodiesel which lead to major differences in the combustion characteristics of the two fuel types. It was found that biodiesel had 10% lower carbon content, almost no sulphur content for biodiesel and up to 12% more oxygen content compared with diesel. This explains the lower caloric value for WCO biodiesel (up to l8 %) compared with diesel. However, higher oxygen content and double bounds in WCO biodiesel increase its susceptibility to oxidation. The CCR test results showed an increase in combustion gas temperature with the increases in biodiesel blend ratio in diesel. This was due to a faster reaction rate for biodiesel than that of diesel leading to a faster brakeage of the hydrocarbon chain to release more heat. The engine tests were performed to measure the torque and emissions for different engine speeds and loads. In general a decrease in engine torque with up to 9% for biodiesel was observed, which was due to the lower calorific value of biodiesel compared with that of diesel. The brake specific fuel consumption (BSFC) increased as the biodiesel blend ratio in diesel increases due a greater mass of fuel being injected at a given injection pressure, compared with diesel. Using WCO blends ratio up to 75% in diesel showed a reduction in exhaust emission compared with diesel, however, at the cost of increased fuel consumption. A common conclusion can be drawn in favour of the WCO biodiesel as being a greener alternative to petro-diesel when used in blend with diesel. However, due to large variations in the biomass used for biodiesel production could lead to variations in physical and chemical properties between biodiesel produced from different biomass. Therefore more stringent standards need to be imposed for biodiesel quality in order to diminish the effect of variation in physicochemical properties on engine performance and emissions. The future work in developing standard test procedures for establishing fuel properties and limits/targets would be beneficial in using a large amount of waste cooking oil in the production of biodiesel, thus contributing to reduction in CO2 and waste minimisation.

M. Tech. (Department of Chemistry, Faculty of Applied and Computer Science), Vaal University of Technology / Cadmium and cobalt complexes of urea and thiourea were synthesized using ethanol as a solvent. All complexes were refluxed at 70 - 80 °C, left to cool at room temperature, washed with methanol and acetone to remove impurities and dried at an open environment. The characterization of complexes was done using FTIR spectroscopy, elemental analysis and TGA. The complexes were found to coordination with the ligands through sulphur and oxygen atoms to the metal, instead of nitrogen. These were as results of wavelength shifting from high to low frequency from spectra of the complexes as compare to their free ligands. These observations make these complexes good candidates for the possible use in synthesis of metal sulphides or oxides nanoparticles. Thermogravimetric analyses of all the complexes were conducted to check the stability of use as precursors for nanoparticles at low and high temperature. A number of thiourea and urea complexes with cadmium and cobalt have been prepared and used in the preparation of metal sulphides/oxides nanoparticles. Complexes start to decompose at low temperature about 100°C and the last decomposition step was at about 800-900°C, which is convenient to thermal decomposition of precursors in the high boiling solvents or capping agent to prepare surface capped metal sulphides/oxides nanoparticles. The complexes were easy to synthesize, low cost and stable in air and were obtained in reasonable yields. All the complexes reported in this study have been used as single source molecular precursor in the preparation of cadmium oxide, cadmium sulphide, cobalt oxide, cobalt sulphide nanoparticles (normal) and as mixture of any two complexes to form core-shells nanoparticles. Quality nanoparticles synthesis requires three components: precursors, organic surfactants and solvents. The synthesis of the nanoparticles can be thought of as a nucleation event, followed by a subsequent growth period. Both the nucleation and growth rates were found to be dependent upon factors such as temperature, growth time, and precursor concentration. For a continuous flow system the residence time (at nucleation and growth conditions) was also found to be important. In order to separate the nucleation and growth events, injection techniques were employed to achieve rapid nucleation of nanoparticles with final size dictated by the growth temperature and/or residence time through the growth zone of the reaction system. Good crystalline normal nanoparticles were obtained from thermolysis of the precursors in hexadecylamine (HDA) as the capping agent at fixed concentrations, temperature and time. All nanoparticles showed a blue-shift in band edges with good photoluminescence behaviour which is red-shifted from their respective band edges and XRD patterns, the crystal structure are in hexagonal phase. The particles showed rods, spheres and hexagonal shapes. Nucleation and growth mechanism brings new avenue in nanostructures called core-shells, which have been reported to have improved luminescence, quantum yields, decreased fluorescence lifetimes, and benefits related to the tailoring of the relative band-gap positions between the two materials. In this study cadmium and cobalt complexes of urea and thiourea were separately dispersed in TOP and injected separately (allowing nucleation/core to occur, followed by the shell) in hot HDA at 180ºC for 1hour to yield core-shell nanoparticles. Parameters, such as concentration, temperature and capping molecule as factor affecting nucleation and growth of the core-shells were monitored. The core-shell nanoparticles were characterized by UV/Vis spectroscopy, XRD and TEM. We observed spherical, tripod, bipods, hexagonal and irregular shaped nanoparticle as the concentration of the precursors was increasing, however we were able to form core-shells nanoparticles in one set of experiment 1:3 CdS-CdO, which are assumed to be a reverse type I coreshells nanoparticles. Exciton absorption peaks at higher energy than the fundamental absorption edge of bulk indicate quantum confinement effect in nanoparticles as a consequence of their small size. XRD patterns, crystals range from hexagonal, cubic and mixture of hexagonal and orthorhombic. A low temperature studies were also conducted a mixture of hexagonal and sphererical shapes with sheets like onion morphology were observed. / NRF HUB & SPOKES (VUT)

Cette étude est consacrée aux monnaies d’or et d’argent lagides comme moyen de l’action des rois d’Alexandrie entre l’avènement de Ptolémée V en 204 et la mort de Ptolémée IX en 81. Ce grand deuxième siècle est habituellement considéré comme un temps de crise profonde du pouvoir royal, alors aux prises avec des révoltes en Égypte, des luttes dynastiques et affaibli par la perte de la plupart des territoires extérieurs hormis Chypre et Cyrène. Dans ce contexte, la place et le rôle des émissions ptolémaïques dans la gestion du royaume par les Ptolémées peuvent être questionnés. Pour cela, nous avons répertorié 6 413 pièces au sein d’un catalogue dans le but de collecter un maximum d’informations ainsi que pour réaliser une étude des niveaux de production tout au long de la période. A cela s’ajoute l’établissement d’un catalogue des trésors et trouvailles isolées remis à jour. Une deuxième partie est dédiée à l’importance ainsi qu’aux classements de ces émissions qui sont discutés et parfois révisés au regard des informations réunies. Pour cela, les 380 analyses élémentaires de monnaies d’or et d’argent réalisées à l’IRAMAT fournissent une somme d’informations inédites. Enfin, nous tentons d’insérer les nouvelles données produites dans les connaissances générales de l’histoire du royaume des Ptolémées au IIe siècle. L’enjeu est de déterminer dans quelle mesure l’usage de la monnaie peut être un révélateur des politiques royales. Il convient également de définir l’importance de ce moyen de paiement et dans quels cas il est employé. Ainsi, le témoignage des monnaies permet d’analyser certains aspects de la réaction du pouvoir royal lagide face aux difficultés rencontrées au IIe siècle. / This study is dedicated to the Ptolemaic gold and silver coins as means of action of kings of Alexandria from the advent of Ptolemy V in 204 until the death of Ptolemy IX in 81. This expanded second century is usually considered as a time of deep crisis of the royal power, then battling against internal revolts in Egypt, dynastic fights and weakened by the loss of most of the foreign territories except Cyprus and Cyrene. In this context, the place and the role of the Ptolemaic issues in the management of the kingdom by the Ptolemies can be questioned. We listed 6 413 coins within a catalog to collect a maximum of information there as well as to realize a study of the levels of production throughout the all period. Then, an updated catalog of hoards and isolated finds is added. The second part is dedicated to the whole importanceas well as to the classifications of these broadcast issues which are discussed and sometimes revised with regards to the information gathered. For that purpose, the contribution of 380 elemental analysis of gold and silver coins achieved in the IRAMAT laboratory supplies a sum of new information. Finally, we try to insert the new data produced intothe general knowledge of the history of the Ptolemaic kingdom in the second century. The stake is to determine to what degree the use of coins can reflect the royal policies. It is also advisable to define the importance of this means of payment and in which cases it is used. In the end, the testimony of coinage allows us to analyze certain aspects of the reaction of the Ptolemaic royal power confronting difficulties met in the second century.

PIXE, Particle Induced X-ray Emission, est une méthode d’analyse multiélémentaire, rapide, non destructive, basée sur la détection des rayons X caractéristiques émis suite à l’interaction de particules chargées avec la matière. Cette méthode est usuellement utilisée avec des protons accélérés à une énergie de l’ordre de quelques MeV dans des domaines d’applications variés, atteignant une limite de détection de l’ordre de quelques μg/g (ppm). Cependant, la profondeur d’analyse est relativement limitée. Grâce au cyclotron ARRONAX, nous pouvons utiliser des protons ou des particules alpha jusqu’à une énergie de 70 MeV pour mettre en œuvre la technique PIXE à haute énergie. Avec de telles énergies, nous excitons préférentiellement les raies X K, plus énergétiques que les raies L utilisées dans la PIXE classique pour l’analyse des éléments lourds. L’analyse d’échantillons épais, en profondeur, est ainsi accessible. Pour l’analyse des éléments légers, nous pouvons utiliser la détection de rayons gamma émis pas les noyaux excités en combinant les méthodes PIGE et PIXE. Nous allons tout d’abord présenter les caractéristiques et les principes d’analyse de la méthode PIXE à haute énergie que nous avons développée à ARRONAX. Nous détaillerons ensuite les performances atteintes, notamment en termes de limite de détection dans différentes conditions expérimentales. Enfin, nous présenterons les résultats obtenus pour l’analyse d’échantillons multicouches et la quantification d’éléments traces dans des échantillons épais. / Particle Induced X-ray Emission (PIXE) is a fast, nondestructive, multi-elemental analysis technique. It is based on the detection of characteristic X-rays due to the interaction of accelerated charged particles with matter. This method is successfully used in various application fields using low energy protons (energies around few MeV), reaching a limit of detection of the order the μg/g (ppm). At this low energy, the depth of analysis is limited. At the ARRONAX cyclotron, protons and alpha particles are delivered with energy up to 70 MeV, allowing the development of the High Energy PIXE technique. Thanks to these beams, we mainly produce KX-rays, more energetic than the LX-rays used with standard PIXE for the heavy elements analysis. Thus, in depth analysis in thick materials is achievable. For light element analysis, the PIGE technique, based on the detection of gamma rays emitted by excited nuclei, may be used in combination with PIXE. First of all, we will introduce the characteristics and principles of high energy PIXE analysis that we have developed at ARRONAX. Then we will detail the performance achieved, particularly in terms of detection limit in various experimental conditions. Finally, we present the results obtained for the analysis of multilayer samples and quantification of trace elements in thick samples.