<p>Thallium is a highly toxic element that humans are exposed to mainly by consumption of drinking water and vegetables grown in soil with high thallium content but also through inhalation of particles in the air. Thallium is also present in fossil fuels, alloys, and in electronic utilities. The increasing use of the element and emissions from notably energy production has lead to a higher load on the surface of the Earth. This study aims at increasing the knowledge about the behaviour of thallium in aquatic environments. Focus has been on the redox chemistry of thallium in relation to its mobility, which is of great importance because Tl(I) and Tl(III) have very different properties in this respect.</p><p>The relationship between Tl(I) and Tl(III) in surface waters from contaminated and uncontaminated environments was examined by ion chromatography connected on line to ICP-MS (inductively coupled plasma mass spectrometry). It was found in controlled systems that even though Tl(III) is thermodynamically unstable under fresh water conditions Tl(I) was oxidised in the presence of light and iron(III). This was also confirmed in field studies. When lake water samples were exposed to light, Tl(I) was oxidised and thallium was lost from the solution. The most likely explanation for this was adsorption of thallium to particle surfaces.</p><p>The concentration of thallium in Swedish lakes and soil were measured. In unpolluted lakes the concentration ranges between 4.5-12 ng/l, the sediment concentration was 0.07-1.46 mg/kg. The anthropogenic load was found to have increased since the end of the Second World War although concentrations above background were found since the early industrialisation. In contaminated areas the concentration in soil ranges from 0.64-88 mg/kg, high concentrations were found in systems with alum shale and in soil exposed to runoff from a lead and zinc enrichment plant.</p><p>The mobilisation of thallium from solid phases in contaminated areas was dependent on pH and about 50% of the leachable content was mobilised already at pH 5-6. Once it had been released to water it was highly mobile. These conditions suggest that in a large part of the Swedish environment a high mobility of thallium can be expected.</p>

<p>The performance of different types of nebulisers: Vulkan direct injection nebuliser (Vulkan DIN), direct injection high efficiency nebuliser (DIHEN), microconcentric nebuliser coupled to cyclonic or double pass spray chamber (MCN-C or MCN-DP, respectively) was investigated and compared when used for sample introduction to ICP-MS or ICP-OES. With ICP-OES, in axial viewing mode, intensity distributions across the radius of the plasma (radial intensity profiles) were determined for different spectral lines with Esum 1.85-15.41 eV to determine fundamental plasma properties for various matrices using Vulkan DIN and MCN-C. The results showed that with the MCN-C the ionisation temperature (Tion) was about the same across the measured region of the plasma (±3.0 mm) whereas with the Vulkan DIN the Tion was significantly lower in the centre of the plasma. A large deviation from local thermodynamic equilibrium, as well as deteriorated stability, was observed for the plasma when using the Vulkan DIN.</p><p>With ICP-MS noise power spectra (NPS) were generated to identify sources of noise. NPS showed that the magnitude of white noise for the tested sample introduction systems decreased in the following order: Vulkan DIN > DIHEN > MCN-C > MCN-DP. This order follows the decrease of mean droplet size and span of the size distribution, indicating that the white noise is caused by spatial and temporal non-uniform desolvation and ionisation. Another source of noise arose from the peristaltic pump and the magnitude of pump interference noise decreased in the following order: DIHEN > MCN-C/DP > Vulkan DIN. Mains power interference noise and 1/f noise were lower for the direct injection nebulisers compared to the spray chamber systems. The contribution or effects of these noise components on relative standard deviations of steady-state ion-count rate and isotope ratio measurements is discussed in this thesis.</p><p>Aerosols generated by the Vulkan DIN and the DIHEN were also directly characterised using Particle Dynamic Analysis. The Vulkan DIN produced particles with a mean diameter of ~30 µm and a size distribution between 2-80 µm. With the DIHEN the corresponding values were ~11 µm and 1-40 µm, respectively, with a few particles at 55-78 µm. The mean velocity of particles from the Vulkan DIN was ~10 m s-1 and from the DIHEN ~18 m s-1. The lower velocity allows longer residence time counteracting the effects of the larger droplet size.</p>

Ph.D. / Electrical Engineering / A novel combinatory on-line technique coupling Electrochemistry (EC) with Inductively Coupled Plasma - Mass Spectrometry (ICP-MS) for in-situ quantitative determination of the corrosion mechanism in magnetic thin film structures has been developed in this research. Detailed construction of a system and a comprehensive methodology was described in this dissertation. Uniformly coated multi-layer magnetic thin film samples with multi-elemental alloys containing CoCrPtB and CrMo/Cr on the Ni/P substrate were used in this research for demonstrations. In-situ quantifications conducted in a series of experiments revealed that elemental dissolution was a predominant mechanism during corrosion courses of metallic thin film materials. At the microscopic scale, using results from depletion rate determination as well as cross-sectional analyses of microstructures and magnetic features, elemental passivity was observed to occur, depending on corrosion conditions. Without external influences, surface topographic measurements indicated that passive film could be produced at the macro-scale. The dependence of the dissolution rate of each metallic ion of alloys on electrolyte concentration, potential bias, scanning rate, and corrosion duration suggested that the most critical influential factor in corrosion mechanisms was epitaxial microstructures with strongly-oriented arrangements of grains and grain boundaries. Through the use of cross-sectional microstructural analysis, including high resolution TEM micrography, electron FFT diffraction, and nano-probe with EDS profiling, variations of elemental spatial distributions at grains and grain boundaries due to the corrosion phenomena were discovered, which provided a comprehensive understanding of occurrences of micro-corrosion in thin film structures. Because of the unique magnetic property of magnetic thin films, extensive studies of field strengths from the surface were also performed in this research. Important magnetization variations were noticed when cross-sectional images were obtained. Finally, models of corrosion kinetics in the multiple layers of magnetic thin film structures were proposed.

La Mine Colombia, située dans le District Aurifère d'El Callao, Venezuela, est considérée comme un gisement de type "géant" (i.e. > 500 t Au) car les réserves prouvées sont égales à 23 millions d'onces (= 740 t Au), ce qui fait de ce gisement le plus gros gisement du Craton Guyanais. La minéralisation est encaissée dans des formations basaltiques d'âge paléoprotérozoïque présentant toutes les caractéristiques des basaltes de plateau océanique. La minéralisation se localise au niveau de trois filons sécants sur la foliation, appelés "veine de quartz aurifère Colombia, América et Hansa". Ces "veines" sont en fait constituées par un réseau interconnecté de veines de quartz mais aussi d'ankérite et d'albite, délimitant une caisse filonienne, qui peut être définie par un mur et un toit, dans laquelle le réseau de veines englobe de nombreux fragments de basalte fortement pyritisés. L'or se rencontre quasi-systématiquement dans les fragments de métabasalte, en relation étroite avec la pyrite. Nous considérons ces systèmes de veines comme des "corridors" de déformation minéralisés, qui se seraient formés dans le domaine de transition fragile-ductile, en présence d'un même fluide hydrothermal à H2O-CO2-NaCl et à faible salinité. Ces corridors minéralisés, se formeraient en relation avec une succession de microséismes, à chaque microséisme, une nouvelle génération de pyrite cristalliserait dans les fragments de basalte. Cette pyrite renfermerait systématiquement de l'or soit en substitution dans le réseau cristallin du cristal, soit sous forme de nano-inclusions de sulfosels polymétalliques ; cet or " invisible " représenterait l'or primaire du gisement. De ce fait, nous considérons que l'essentiel de l'or "visible" du gisement serait secondaire et le produit de la remobilisation de l'or primaire "invisible". Nous considérons que cet événement tardif de déformation dans l'orogenèse Transamazonienne est primordial pour avoir des grains d'or visibles et donc un gisement économiquement exploitable.

The performance of different types of nebulisers: Vulkan direct injection nebuliser (Vulkan DIN), direct injection high efficiency nebuliser (DIHEN), microconcentric nebuliser coupled to cyclonic or double pass spray chamber (MCN-C or MCN-DP, respectively) was investigated and compared when used for sample introduction to ICP-MS or ICP-OES. With ICP-OES, in axial viewing mode, intensity distributions across the radius of the plasma (radial intensity profiles) were determined for different spectral lines with Esum 1.85-15.41 eV to determine fundamental plasma properties for various matrices using Vulkan DIN and MCN-C. The results showed that with the MCN-C the ionisation temperature (Tion) was about the same across the measured region of the plasma (±3.0 mm) whereas with the Vulkan DIN the Tion was significantly lower in the centre of the plasma. A large deviation from local thermodynamic equilibrium, as well as deteriorated stability, was observed for the plasma when using the Vulkan DIN. With ICP-MS noise power spectra (NPS) were generated to identify sources of noise. NPS showed that the magnitude of white noise for the tested sample introduction systems decreased in the following order: Vulkan DIN &gt; DIHEN &gt; MCN-C &gt; MCN-DP. This order follows the decrease of mean droplet size and span of the size distribution, indicating that the white noise is caused by spatial and temporal non-uniform desolvation and ionisation. Another source of noise arose from the peristaltic pump and the magnitude of pump interference noise decreased in the following order: DIHEN &gt; MCN-C/DP &gt; Vulkan DIN. Mains power interference noise and 1/f noise were lower for the direct injection nebulisers compared to the spray chamber systems. The contribution or effects of these noise components on relative standard deviations of steady-state ion-count rate and isotope ratio measurements is discussed in this thesis. Aerosols generated by the Vulkan DIN and the DIHEN were also directly characterised using Particle Dynamic Analysis. The Vulkan DIN produced particles with a mean diameter of ~30 µm and a size distribution between 2-80 µm. With the DIHEN the corresponding values were ~11 µm and 1-40 µm, respectively, with a few particles at 55-78 µm. The mean velocity of particles from the Vulkan DIN was ~10 m s-1 and from the DIHEN ~18 m s-1. The lower velocity allows longer residence time counteracting the effects of the larger droplet size.

This thesis deals with the reliability of methods for the speciation of mercury in environmental and biological samples. Problems with speciation methods that couple chromatography to atomic spectrometric detection and how to overcome the problems are discussed. Analytical techniques primarily studied and evaluated are high performance liquid chromatography-cold vapour-atomic absorption spectrometry (HPLC-CV-AAS), HPLC-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS), capillary electrophoresis-ICP-MS (CE-ICP-MS) and gas chromatography-ICP-MS (GC-ICP-MS). Applying a multi-capillary approach increased the analyte amount injected into a CE-ICP-MS system and improved the overall sensitivity. A microconcentric nebulizer with a cyclone spray chamber was shown to improve the detection limits for mercury species 3-13 times in HPLC-ICP-MS and 11-19 times in CE-ICP-MS compared to a cross-flow nebulizer with a Scott spray chamber. To decrease the interference of water vapour in HPLC-CV-AAS a Nafion dryer tube was inserted between the CV-generation and the detector. Methyl mercury was however lost in the Nafion unless it was reduced to elemental mercury prior transport through the dryer tube. During sample pre-treatment, incomplete extraction, losses and transformation (alkylation, dealkylation, oxidation and reduction) of mercury species can lead to significant errors (underestimation and overestimation) in the determination of the concentrations. Methods to detect and determine the degree of transformation as well as correct for errors caused by transformation are presented in the thesis. The preferable method use species-specific enriched stable isotope standards in combination with MS detection and a matrix based calculation scheme. This approach is very powerful as both the concentrations of the species as well as the degrees of transformation can be determined within each individual sample.

Brominated organic compounds (BOCs) of both natural and anthropogenic origin are abundant in the environment. Most compounds are either clearly natural or clearly anthropogenic but some are of either mixed or uncertain origin. This thesis aims to identify some naturally produced BOCs and to develop a method for analysis of the bromine isotopic composition in BOCs found in the environment. Polybrominated dibenzo-p-dioxins (PBDDs) in the Baltic Sea are believed to be of natural origin although their source is unknown. Since marine sponges are major producers of brominated natural products in tropical waters, BOCs were quantified in a sponge (Ephydatia fluviatilis) from the Baltic Sea (Paper I). The results showed that the sponge does not seem to be a major producer of PBDDs in the Baltic Sea. In this study, mixed brominated/chlorinated dibenzo-p-dioxins were however discovered for the first time in a background environment without an apparent anthropogenic source. The use of nuclear magnetic resonance spectroscopy (NMR) is unusual in analytical environmental chemistry due to its sample requirements. Preparative capillary gas chromatography was used to isolate a sufficient amount of an unidentified BOC from northern bottlenose whale (Hyperoodon ampullatus) blubber (Paper II) to enable NMR analysis for identification of the compound. The bromine isotopic composition of BOCs may give information on the origin and environmental fate of these compounds. The first steps in this process are the development of a method to determine the bromine isotope ratio in environmentally relevant BOCs (Paper III) and measuring the bromine isotope ratio of several standard substances to establish an anthropogenic endpoint (Paper IV). / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.

La faïence est une céramique caractérisée par son revêtement vitreux blanc opaque, grâce à l'adjonction d'oxyde d'étain ; sur ce fond on peut apposer les décors polychromes. Résultant d'une technologie abbaside (VIIIe siècle), elle connait son apogée en France au XVIIIe siècle. Les précédentes études menées sur la faïence moderne ont mis en évidence la nécessité de procéder à une approche pluridisciplinaire pour appréhender ce matériau complexe, ses techniques de fabrication, et cerner les enjeux de sa production. Ce travail de recherche s'inscrit dans la continuité pour s'élargir aux productions faïencières du Sud Ouest de la France quelques peu délaissées du point de vue archéométrique. La manufacture Babut, première faïencerie établie à Bergerac, fut sélectionnée dans ce but. La production perdure sur cinquante ans environ, jusqu'à la Révolution Française.En prenant en considération ces observations, cette thèse a permis tout d'abord d'identifier la production du point de vue des matériaux et des techniques, de mettre en place un référentiel géochimique, ainsi qu'établir un corpus stylistique de base pour cette manufacture. Ensuite l'étude a porté sur l'évaluation du potentiel de méthodes d'analyses non destructives pour l'attribution de provenance directe à partir de la surface des glaçures. Et enfin ce travail a permis d'examiner la place de la faïence bergeracoise et de sa production au sein du tissu industriel régional, et les replacer dans le contexte plus général de la production faïencière française à l'aube de la Révolution industrielle.

Les apports atmosphériques sont suspectés de jouer un rôle important dans les processus biogéochimiques des régions océaniques HNLC. Des échantillons de dépôt atmosphérique total et d'aérosols ont été collectés en continu entre 2009 et 2010 dans l'océan austral indien, aux îles Kerguelen et de Crozet. Ils ont été mesurés par HR-ICP-MS. Les concentrations en surface des aérosols terrigènes sont basses et ne peuvent rendre compte des flux de dépôt de poussières qui sont plus élevés que ceux précédemment observés pour la région mais qui restent en adéquation avec les modèles atmosphériques. Le calcul des coefficients d'abattement suggère que l'aérosol mesuré en surface n'est pas représentatif de celui qui va générer le dépôt et qui est présent plus haut dans la colonne troposphérique, ce qui interdit ici l'estimation du flux à partir de ces mesures. Les flux de dépôt ont été établis pour une large gamme d'éléments identifiés comme venant de source terrigène ou marine. Pour certains d'entre eux (Pb, As, ...), une contribution anthropique a été observée pendant l'hiver austral. Les flux des éléments crustaux Al, Fe, Mn et Si sont similaires pour Kerguelen et Crozet ; ceux des autres éléments non marins sont différents d'un facteur deux à cinq avec un gradient décroissant de Crozet aux Kerguelen. Les rapports isotopiques de plomb montrent que le dépôt reçu aux Kerguelen provient principalement d'Amérique du sud ; le dépôt à Crozet semble fortement influencé par les apports africains. Les profils de REE pourraient confirmer ces observations. Les concentrations de métaux sont très basses dans les pluies avec une solubilité très élevée.

Selenium (Se) is an element with important health implications that is emitted in significant amounts from volcanoes. Attracted by the fertility of volcanic soils, around 10% of the world population lives within 100 km of an active volcano. Nevertheless, the behaviour of Se in volcanic environments is poorly understood. Therefore, the main aim of this thesis is to investigate the role of soils in the Se cycling in volcanic environments. Prior to the geochemical studies, precise and accurate methods for the determination of Se contents, speciation and isotopic signatures were developed. Afterwards, a combination of field studies and lab controlled experiments were performed with soils from two contrasting European volcanic settings: Mount Etna in Sicily (Italy) and Mount Teide in Tenerife (Spain). The results showed a strong link between Se behaviour and soil development, indicating that Se mobility in volcanic soils is controlled by sorption processes and soil mineralogy. / El selenio (Se) tiene afectas sobre la salud y es emitido por los volcanes. Atraída por la fertilidad de los suelos volcánicos, un 10% de la población mundial vive <100 km de volcanes activos. Sin embargo, el comportamiento geoquímico del Se en ambientes volcánicos es aún poco conocido. El objetivo de esta tesis es contribuir a la comprensión del papel del suelos en el ciclo del Se en medios volcánicos. En una primera etapa se desarrollaron métodos analíticos para determinar el contenido, la especiacíon y las relaciónes isotópicas del Se. Los estudios geoquímicos se realizaron con suelos de dos lugares con características muy distintas: el Monte Etna (Italia) y el volcán Teide (Tenerife). Los estudios de terreno y de laboratorio revelaron una gran interrelación entre el comportamiento del Se y el desarrollo de suelos, y que la movilidad de Se está controlado por los procesos de adsorción y la mineralogía en suelos volcánicos.