Carbonatites are unique and enigmatic magmatic rocks of unclear origin, with very specific mineralogy and geochemical properties. They are predominantly composed of magmatic calcite or other carbonate minerals (Le Bas 1987) and have low content of SiO2 (Le Maitre 2002). Origin of these peculiar magmas is still not clear but they appear to represent an important "window" into processes in Earth's mantle. They are considered either as residual melts from a fractionated carbonated nephelinite or melilitite (Gittins 1989; Gittins and Jago 1998), as immiscible fractions of CO2-saturated silicate melts (Freestone and Hamilton 1980; Amundsen 1987; Kjarsgaard and Hamilton 1988, 1989; Brooker and Hamilton 1990; Kjarsgaard and Peterson 1991; Church and Jones 1995; Lee and Wyllie 1997; Dawson 1998; Halama et al. 2005; Brooker and Kjarsgaard 2011), or as primary melts which are were generated from CO2-bearing peridotite through partial melting (Wallace and Green 1988; Sweeney 1994; Harmer and Gittins 1998; Harmer et al. 1998; Ying et al. 2004). Abundances of rare earth elements (REE) are often high in carbonatites because carbonatitic magmas can dissolve these elements much easily than silicate magmas (Nelson et al. 1988). Carbonatitic magma can also dissolve large quantities of Sr, Ba, P and mainly Zr and Nb,...

Etudier le rôle des éléments traces à l’échelle cellulaire requiert des outils analytiques de pointe. Nous avons développé une nouvelle méthodologie précise de la répartition des éléments chimiques cellulaires à partir d’une combinaison des méthodes d’analyse par faisceaux d’ions PIXE, RBS et STIM. Cette méthodologie s’appuie fortement sur le développement d’un logiciel (Paparamborde) pour le traitement quantitatif des expériences STIM. La validité de cette méthode ainsi que ses limites sont discutées. La méthode STIM-PIXE-RBS permet de quantifier la composition en éléments traces (µg/g) avec une incertitude de mesure évaluée à 19,8% dans des compartiments cellulaires de masse inférieure à 0,1 ng.Une des limites de la méthode réside dans le faible nombre d’échantillons analysables en raison à la fois du temps minimum nécessaire pour réaliser une acquisition et de l’accès limité aux plateformes d’analyse par faisceaux d’ions. C’est pourquoi nous avons également développé une base de données pour la capitalisation des compositions chimiques cellulaires (BDC4). Cette base de données s’inscrit dans la logique de l’utilisation de la composition chimique cellulaire comme un traceur de l’activité biologique, et doit permettre à terme de définir des compositions chimiques de référence pour les différents types cellulaires analysés.L’application de la méthodologie STIM-PIXE-RBS à l’étude de la toxicologie nucléaire du cobalt permet d’illustrer son intérêt en pratique. En particulier, l’analyse STIM s’avère indispensable dans le cas d’échantillons présentant une perte de masse organique au cours de l’analyse PIXE-RBS. / The study of the role of trace elements at cellular level requires the use of state-of-the-art analytical tools that could achieve enough sensitivity and spatial resolution. We developed a new methodology for the accurate quantification of chemical element distribution in single cells based on a combination of ion beam analysis techniques STIM, PIXE and RBS. The quantification procedure relies on the development of a STIM data analysis software (Paparamborde). Validity of this methodology and limits are discussed here. The method allows the quantification of trace elements (µg/g) with a 19.8 % uncertainty in cellular compartments with mass below 0.1 ng.The main limit of the method lies in the poor number of samples that can be analyzed, due to long irradiation times required and limited access to ion beam analysis facilities. This is the reason why we developed a database for cellular chemical composition capitalization (BDC4). BDC4 has been designed in order to use cellular chemical composition as a tracer for biological activities and is expected to provide in the future reference chemical compositions for any cellular type or compartment.Application of the STIM-PIXE-RBS methodology to the study of nuclear toxicology of cobalt compounds is presented here showing that STIM analysis is absolutely needed when organic mass loss appears during PIXE-RBS irradiation.

Summary Serpentinites from the northern Vermont were examined for the distribution and abundance of As. XRD and electron microprobe showed the samples are composed of antigorite, chromite, magnetite, and carbonate minerals (magnesite, dolomite, calcite). The concentration in As when the samples were dissolved in H3PO4 was 10% of the concentration in As when the samples were dissolved in concentrated HF/HNO3, suggesting that As is mainly incorporated in the structure of antigorite. X-ray absorption near-edge structure spectra showed that the As is As(III) in the samples. Extended X-ray absorption fine structure spectra suggested that the As has a tetrahedral coordination and is located in the Si-site in serpentine.

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.

Les chondres, sphérules infra-millimétriques composées de minéraux silicatés de haute température, sont les constituants majeurs des météorites primitives. Ils présentent d'importantes variabilités texturales et chimiques révélatrices d'une histoire complexe. Cette thèse s'est intéressée à la chronologie de formation des chondres et de leurs précurseurs à deux échelles de temps distinctes aux moyens de deux approches complémentaires : la géochimie isotopique via le chronomètre isotopique à courte période ²⁶lAl-²⁶Mg et la pétrologie expérimentale. Le développement au cours de cette thèse d'un protocole analytique innovant de mesure in situ de haute précision par sonde ionique des compositions isotopiques du Mg et Al, a permis de démontrer l'homogénéité de la distribution de l'²⁶Al dans le disque d'accrétion, ce qui présente d'importantes implications sur la chronologie relative et les processus de formation des chondres, mais aussi sur l'origine de l'²⁶Al dans le Système Solaire. L'application de ce protocole analytique aux olivines reliques des chondres permet de préciser leur origine, ainsi que leur chronologie et leur processus de formation. Les expérimentations permettent de montrer qu'il est aisé de former des analogues de chondres de type II PO à partir de chondres de type I PO. Un tel processus de formation des chondres implique l'application de régimes thermiques isothermes suivis d'une trempe rapide, incompatibles avec les mécanismes classiques d'ondes de choc. D'autre part, nous montrons que les compositions chimiques en éléments majeurs et traces des différents types de chondres porphyriques peuvent être reproduites par le mélange de trois phases réfractaires solides héritées des précurseurs des chondres (olivine réfractaire, liquide réfractaire et métal) et d'une phase gazeuse riche en éléments volatils et modérément volatils. Ces résultats nous ont conduit à proposer un modèle de filiation entre les chondres / Chondrules are the major constituent of primitive meteorites. The large variability of textures and chemical compositions within chondrules is indicative of a complex history. This work is focused on the chronology of formation of chondrules and of their precursors by using two complementary tools: the short-lived radio-isotopes ²⁶Al-²⁶Mg and the experimental petrology.The development of a high precision analytical methodology for in situ measurements of the Mg and Al isotopic compositions by ion probe allows to demonstrate that the distribution of ²⁶Al was homogeneous within the accretion disk. This result has important implications for the chronology and process of chondrule formation and also for the origin of ²⁶Al in the Solar System. By using the same methodology with relict olivines in chondrules, we were able to constrain their origin and their formation process.From experimental petrology studies, we show that it was easy to form type II PO chondrules analogues from type I PO analogues. Such a process for chondrules formation implies an isothermal heating followed by a quick quench which is incompatible with the classical shock-waves model. Moreover, we show that the chemical compositions for major and trace elements of the different types of porphyritic chondrules can be easily reproduced by a mixing model composed of three refractory phases inherited from chondrules precursors (refractory olivine, refractory liquid and iron metal) and a gas phase enriched in volatile and moderately volatile elements. Finally, we propose a model of genetic linkage between the different types of porphyritic chondrules

A presente dissertação apresenta uma investigação sobre a evolução tectono-metamórfica da Formação São Tomé, uma das unidades metassedimentares pertencente ao Grupo Rio Doce, no Orógeno Araçuaí. Essa unidade, de origem pelítica, ocorre em uma faixa com direção geral aproximadamente N-S, com vergência para NE, contrária ao cráton São Francisco neste setor do orógeno. Possui como litotipo principal quartzo-mica xisto, com proporções variadas de granada, estaurolita, sillimanita e plagioclásio. Duas fases deformacionais estão registradas através de uma foliação continua S1 do tipo clivagem de fratura e uma foliação S2 de clivagem de crenulação. As relações texturais indicam que parte das fases minerais se cristalizaram tanto durante o evento deformacional como em condições ausentes de tensão deviatórica, e registro de condições de pico metamórfico de 6 kbar e 650 °C. Os dados geocronológicos foram obtidos em monazita por meio de datações Th-UPb em microssonda eletrônica. Foram identificadas três populações distintas: (i) A população mais antiga de 641±32 Ma, 614±39 Ma e 607±47 Ma, a qual pode representar grãos detríticos de corpos ígneos, não mais aflorantes, relacionados a um possível estagio pré-colisional ou, tratar-se de monazitas metamórficas formadas em um primeiro evento térmico; (ii) População com idades intermediárias entre 560±32 Ma e 559±29 Ma, compatíveis com as idades do ápice metamórfico regional; (iii) População mais jovem de idades entre 501±28 Ma e 491±34 Ma, condizentes com a formação concomitante à geração dos corpos ígneos tardios. Ainda que não esteja esclarecido se essas idades estão relacionadas a eventos metamórficos distintos ou são reflexo da baixa taxa de resfriamento do orógeno, os três grupos de monazita com idades distintas estão bem estabelecidos. / The present dissertation presents an investigation on the tectono-metamorphic evolution of the São Tomé Formation, one of the metasedimentary units belonging to the Rio Doce Group, in the Araçuaí Orogen. This unit, of pelitic origin, occurs in a band with general direction approximately N-S, with vergence for NE, contrary to the São Francisco craton in this sector of the orogen. It has quartz-mica schist as main lithotype, with varying proportions of grarnet, staurolite, sillimanite and plagioclase. Two deformational phases are recorded through a continuous foliation S1 of the fracture cleavage type and a foliation S2 of crenulation cleavage. The textural relations indicate that part of the mineral phases crystallized both during the deformational event and in conditions absent of deviatore voltage, and record of metamorphic peak conditions of 6 kbar and 650 ° C. The geochronological data were obtained in monazite by means of Th-U-Pb dating in electron microprobe. Three distinct populations were identified: (i) The oldest population of 641 ± 32 Ma, 614 ± 39 Ma and 607 ± 47 Ma, which may represent detrital grains of igneous bodies, no longer outcrops, related to a possible pre- collisional or, being metamorphic monazites formed in a first thermal event; (ii) Populations with intermediate ages between 560 ± 32 Ma and 559 ± 29 Ma, compatible with regional metamorphic apex ages; (iii) Younger population between 501 ± 28 Ma and 491 ± 34 Ma, consistent with the formation concomitant with the generation of late igneous bodies. Although it is unclear whether these ages are related to distinct metamorphic events or are reflective of the low orogenic cooling rate, the three monazite groups of different ages are well established.

Neste trabalho é apresentado um instrumento para auxílio à tomada de decisão em processos que envolvem avaliações da resistência do solo à penetração de raízes. Seu desenvolvimento fundamenta-se na concepção de uma nova ferramenta instrumental avançada, que viabiliza em tempo quase real informações para análise da variabilidade espacial da resistência do solo à penetração de raízes, tanto para área como para perfil, devido aos processos de compactação natural ou artificial do solo. Ensaios para a medida da resistência do solo à penetração de raízes podem ser realizados tanto em ambiente laboratorial como diretamente em campo agrícola. Para o desenvolvimento utilizou-se o enfoque da instrumentação inteligente, bem como uma microsonda (ângulo de cone de 30º, diâmetro de base de 1,6 mm e comprimento total de 30 mm) sensoriada por célula de carga. Resultados mostram que medidas de resistência do solo à penetração de raízes podem ser realizadas até um limite de (49,03 +/- 0,07) Kgf com resolução de 1,57 Kgf. Adicionalmente, a versatilidade do sistema é verificada para a coleta de dados e interpretação da resistência do solo à penetração de raízes, uma vez que podem ser apresentados na forma de tabelas, gráficos unidimensionais, mapas bidimensionais e mapas tridimensionais. Desta maneira, o sistema possibilita ao usuário uma rápida interpretação sobre o estado de agregação do solo em áreas de cultivo agrícolas. / This work is presented an instrument for decision-making in agricultural processes based on the measurements and mapping of soil resistance to the root penetration. Its development was based on a new and advance instrumentation tool, which enables in almost real-time to acquire the necessary information for spatial variability analysis of the resistance to root of plants penetration in soils, due to, either, natural or artificial compaction soil processes, i.e., not only for an area of soil but also to soil profile. The system allows soil resistance essays for both laboratory and agricultural field. Moreover, intelligent instrumentation concept was focused in the development, as well as a microprobe (30º for the spire angle, 1,6 mm for the base diameter, and 30 mm of total length), sensored by strain-gage transducers. Results have shown that measurements of soil resistance to root of plant penetration are allowed up to the limit of (49,03 +/- 0,07) Kgf, with 1,57 Kgf of resolution. Additionally, the suitability of the system is verified for soil resistance data collection and its interpretation to root plant penetration, since they can be presented in format of tables, one-dimensional graphics, two-dimensional maps and three-dimensional maps. Therefore, this system allows to the users a fast interpretation of soil aggregation state in agricultural areas.

Le fonctionnement du cerveau repose sur la libération de molécules telles que les neurotransmetteurs et les métabolites dans le milieu interstitiel. L’étude de ces molécules est donc primordiale afin de mieux comprendre leur rôle physiologique et pathologique. Pour cela, les biocapteurs enzymatiques implantables sont un outil prometteur de par leurs capacités de détection quantitative, en temps réel et dans les tissus profonds. En fonction des dimensions du biocapteur, l’impact de l’implantation peut avoir des conséquences considérables sur la composition chimique du fluide interstitiel. De plus, chaque implantation induit localement une réaction inflammatoire dite « réaction au corps étranger ». La réduction de ces réactions est indispensable afin d’obtenir des estimations plus précises de la concentration des molécules présentes. Dans ce sens, ce manuscrit exposera deux voies de réduction de l’impact lésionnel dû à l’implantation de biocapteurs. Tout d’abord, il sera présenté la miniaturisation de biocapteurs enzymatiques jusqu’à des diamètres externes inférieurs à 15 µm. Et il sera démontré in vivo que ces biocapteurs ultra miniaturisés ont le potentiel d’être implantés dans le cerveau sans induire de dommages détectables aux tissus et aux vaisseaux sanguins. Ensuite, le développement d’une microsonde fabriquée à l’aide des technologies MEMS couplant une détection électrochimique et optique sera introduit dans le cadre du suivi du fluide interstitiel péri- et intratumoral de glioblastomes modifiés pour émettre de la fluorescence. En intégrant deux types de détection sur une unique micro-aiguille, cette microsonde permet de réduire le nombre d’implantations. Ces deux voies de miniaturisation ouvrent la possibilité de suivre la composition chimique du fluide interstitiel de manière moins invasive, et donc de mieux préserver la physiologie des tissus étudiés dans le cerveau. / Brain function is based on the release of molecules such as neurotransmitters and metabolites into the interstitial fluid. The study of these molecules is essential to better understand their physiological and pathological role. For this purpose, implantable enzymatic biosensors are a promising tool because of their quantitative, real-time and deep tissue detection abilities. Depending on the dimensions of the biosensor, the impact of implantation may have considerable consequences on the chemical composition of the interstitial fluid. In addition, each implantation induces a local inflammatory reaction called "foreign body reaction". The reduction of these reactions is crucial in order to provide more accurate estimations of molecules concentrations present in the interstitial fluid. In this sense, this manuscript will expose two ways of reducing the lesional impact due to the implantation of biosensors. First of all, it will be presented the miniaturization of enzymatic biosensors up to external diameters less than 15 µm. And it will be demonstrated in vivo that these ultra miniaturized biosensors have the potential to be implanted in the brain without inducing detectable damage to tissues and blood vessels. Then, the development of a microprobe fabricated using MEMS technologies combining electrochemical and optical detection will be introduced as part of the monitoring of peri- and intratumoral interstitial fluid from glioblastomes modified to fluoresce. By integrating two types of detection on a single micro-needle, this microprobe reduces the number of implantations. These two miniaturization approaches open up the possibility of following the chemical composition of the interstitial fluid in a less invasive way, and thus of better preserving the physiology of the tissues studied in the brain.

Neste trabalho é apresentado um instrumento para auxílio à tomada de decisão em processos que envolvem avaliações da resistência do solo à penetração de raízes. Seu desenvolvimento fundamenta-se na concepção de uma nova ferramenta instrumental avançada, que viabiliza em tempo quase real informações para análise da variabilidade espacial da resistência do solo à penetração de raízes, tanto para área como para perfil, devido aos processos de compactação natural ou artificial do solo. Ensaios para a medida da resistência do solo à penetração de raízes podem ser realizados tanto em ambiente laboratorial como diretamente em campo agrícola. Para o desenvolvimento utilizou-se o enfoque da instrumentação inteligente, bem como uma microsonda (ângulo de cone de 30º, diâmetro de base de 1,6 mm e comprimento total de 30 mm) sensoriada por célula de carga. Resultados mostram que medidas de resistência do solo à penetração de raízes podem ser realizadas até um limite de (49,03 +/- 0,07) Kgf com resolução de 1,57 Kgf. Adicionalmente, a versatilidade do sistema é verificada para a coleta de dados e interpretação da resistência do solo à penetração de raízes, uma vez que podem ser apresentados na forma de tabelas, gráficos unidimensionais, mapas bidimensionais e mapas tridimensionais. Desta maneira, o sistema possibilita ao usuário uma rápida interpretação sobre o estado de agregação do solo em áreas de cultivo agrícolas. / This work is presented an instrument for decision-making in agricultural processes based on the measurements and mapping of soil resistance to the root penetration. Its development was based on a new and advance instrumentation tool, which enables in almost real-time to acquire the necessary information for spatial variability analysis of the resistance to root of plants penetration in soils, due to, either, natural or artificial compaction soil processes, i.e., not only for an area of soil but also to soil profile. The system allows soil resistance essays for both laboratory and agricultural field. Moreover, intelligent instrumentation concept was focused in the development, as well as a microprobe (30º for the spire angle, 1,6 mm for the base diameter, and 30 mm of total length), sensored by strain-gage transducers. Results have shown that measurements of soil resistance to root of plant penetration are allowed up to the limit of (49,03 +/- 0,07) Kgf, with 1,57 Kgf of resolution. Additionally, the suitability of the system is verified for soil resistance data collection and its interpretation to root plant penetration, since they can be presented in format of tables, one-dimensional graphics, two-dimensional maps and three-dimensional maps. Therefore, this system allows to the users a fast interpretation of soil aggregation state in agricultural areas.

A presente dissertação apresenta uma investigação sobre a evolução tectono-metamórfica da Formação São Tomé, uma das unidades metassedimentares pertencente ao Grupo Rio Doce, no Orógeno Araçuaí. Essa unidade, de origem pelítica, ocorre em uma faixa com direção geral aproximadamente N-S, com vergência para NE, contrária ao cráton São Francisco neste setor do orógeno. Possui como litotipo principal quartzo-mica xisto, com proporções variadas de granada, estaurolita, sillimanita e plagioclásio. Duas fases deformacionais estão registradas através de uma foliação continua S1 do tipo clivagem de fratura e uma foliação S2 de clivagem de crenulação. As relações texturais indicam que parte das fases minerais se cristalizaram tanto durante o evento deformacional como em condições ausentes de tensão deviatórica, e registro de condições de pico metamórfico de 6 kbar e 650 °C. Os dados geocronológicos foram obtidos em monazita por meio de datações Th-UPb em microssonda eletrônica. Foram identificadas três populações distintas: (i) A população mais antiga de 641±32 Ma, 614±39 Ma e 607±47 Ma, a qual pode representar grãos detríticos de corpos ígneos, não mais aflorantes, relacionados a um possível estagio pré-colisional ou, tratar-se de monazitas metamórficas formadas em um primeiro evento térmico; (ii) População com idades intermediárias entre 560±32 Ma e 559±29 Ma, compatíveis com as idades do ápice metamórfico regional; (iii) População mais jovem de idades entre 501±28 Ma e 491±34 Ma, condizentes com a formação concomitante à geração dos corpos ígneos tardios. Ainda que não esteja esclarecido se essas idades estão relacionadas a eventos metamórficos distintos ou são reflexo da baixa taxa de resfriamento do orógeno, os três grupos de monazita com idades distintas estão bem estabelecidos. / The present dissertation presents an investigation on the tectono-metamorphic evolution of the São Tomé Formation, one of the metasedimentary units belonging to the Rio Doce Group, in the Araçuaí Orogen. This unit, of pelitic origin, occurs in a band with general direction approximately N-S, with vergence for NE, contrary to the São Francisco craton in this sector of the orogen. It has quartz-mica schist as main lithotype, with varying proportions of grarnet, staurolite, sillimanite and plagioclase. Two deformational phases are recorded through a continuous foliation S1 of the fracture cleavage type and a foliation S2 of crenulation cleavage. The textural relations indicate that part of the mineral phases crystallized both during the deformational event and in conditions absent of deviatore voltage, and record of metamorphic peak conditions of 6 kbar and 650 ° C. The geochronological data were obtained in monazite by means of Th-U-Pb dating in electron microprobe. Three distinct populations were identified: (i) The oldest population of 641 ± 32 Ma, 614 ± 39 Ma and 607 ± 47 Ma, which may represent detrital grains of igneous bodies, no longer outcrops, related to a possible pre- collisional or, being metamorphic monazites formed in a first thermal event; (ii) Populations with intermediate ages between 560 ± 32 Ma and 559 ± 29 Ma, compatible with regional metamorphic apex ages; (iii) Younger population between 501 ± 28 Ma and 491 ± 34 Ma, consistent with the formation concomitant with the generation of late igneous bodies. Although it is unclear whether these ages are related to distinct metamorphic events or are reflective of the low orogenic cooling rate, the three monazite groups of different ages are well established.