A espectrometria de emissão óptica com plasma induzido por laser (LIBS) constitui um método alternativo para a determinação simultânea de macro e micronutrientes em pastilhas de materiais vegetais. No entanto, pouca informação com relação às condições de fluência e de focalização do laser mais apropriadas para a análise de pastilhas de materiais vegetais são disponíveis na literatura. O objetivo deste trabalho foi avaliar os efeitos da fluência, do diâmetro de focalização do laser e do tamanho das partículas das amostras nas análises de pastilhas de tecidos vegetais por LIBS. O arranjo experimental foi composto por um laser pulsado de Nd:YAG a 1064 nm (pulsos de 5 n\'delta\', 360 mJ, 10 Hz) e os sinais de emissão foram coletados por um telescópio acoplado por fibra óptica ao espectrômetro Echelle com detector ICCD. Os parâmetros instrumentais foram ajustados em 20 pulsos acumulados, 2,0 \'mü\'s de atraso e 5,0 \'mü\'s de integração. Amostras laboratoriais consistiram de pastilhas preparadas com folhas moídas criogenicamente (90 % das partículas < 50 \'mü\'m). Maiores intensidades das linhas Ca I 442,554, Mg I 277,983, P I 213,618, Al I 309,271, B I 249,773, Cu I 324,755, Fe II 261,187, Mn II 257,610 e Zn II 206,200 nm foram obtidas com fluências entre 35 e 60 J cm-2 e diâmetros de focalização entre 600 e 1050 \'mü\'m. O uso de fluências e diâmetros de focalização maiores concorreu para melhorar os coeficientes de variação (CV) das medidas. Fixando-se o diâmetro de focalização em 750 \'mü\'m, observou-se que, para a maioria dos analíticos, o CV das medidas foi reduzido 2 vezes quando a fluência foi alterada de 20 para 50 J cm-2. Nestas condições, estes resultados foram atribuídos à maior massa removida e, conseqüentemente, à amostragem mais representativa. Os coeficientes angulares das curvas de calibração também aumentaram quando a fluência foi acrescida. No entanto, não foram verificadas diferenças significativas nos coeficientes de correlação das curvas de calibração e nos limites de detecção empregando-se 25 e 50 J cm-2. Embora as intensidades dos sinais de emissão aumentem com a fluência, a emissão de fundo também aumenta. Por outro lado, o tamanho das partículas das amostras afeta as eficiências de atomização e excitação no plasma induzido por laser. Quando partículas maiores são parcialmente vaporizadas, os sinais de emissão resultantes dos processos de atomização e excitação das espécies constituintes são menores do que os provenientes de partículas menores. Nesta dissertação, melhorias significativas da intensidade dos sinais de emissão e dos CVs das medidas foram observados quando pastilhas preparadas com partículas < 75 \'mü\'m foram analisadas. Não foram observadas diferenças significativas nas intensidades dos sinais de emissão e no CV das medidas nas análises de pastilhas preparadas com partículas entre 20 e 75 \'mü\'m. Pastilhas preparadas com partículas > 75 \'mü\'m apresentaram problemas de coesão e, após ablação, apresentaram crateras não uniformes. A análise destas pastilhas resultou em CV das medidas geralmente > 15 %. Os resultados obtidos neste trabalho confirmaram que é recomendável utilizar amostras de calibração e amostras-teste com distribuição do tamanho das partículas semelhante para evitar efeitos físicos de matriz, que alteram as interações laser-amostra / Most recently, it was demonstrated that laser induced breakdown spectrometry (LIBS) constitutes an alternative for the simultaneous determination of macro- and micronutrients in pellets of plant materials. However, there is no information regarding the most appropriate fluence and laser focusing for analysis of pellets of plant materials. The aim of this work was to evaluate the effect of laser focusing and fluence on LIBS analysis of plants. The effect of particle size on LIBS analysis of pellets of plant materials as well as sample preparation approaches were also discussed. The experimental setup was designed by using a Q-switch Nd:YAG laser (5 n\'delta\', 360 mJ, 10 Hz, _ \'lâmbda\' = 1064 nm) and the emission signals were collected by lenses into an optical fiber coupled to an echelle spectrometer equipped with a high-resolution ICCD. Instrumental parameters consisted of 20 accumulated laser pulses, 2.0 \'mü\'s delay time and 5.0 \'mü\'s integration time gate. Pellets prepared from cryogenically ground plant leaves (90 % particles < 50 \'mü\'m; median = 10 \'mü\'m) were used as laboratory samples and 6 laser spot diameters (from 180 to 1050 \'mü\'m) at different laser fluences were evaluated. Results indicate that elements emission intensities increased with both laser fluence and spot diameter. Higher intensities for Ca I 442.554, Mg I 277.983, P I 213.618, Al I 309.271, B I 249.773, Cu I 324.755, Fe II 261.187, Mn II 257.610, and Zn II 206.200 nm emission lines were observed with fluences in the 35 - 60 J cm-2 range and spot diameters between 600 and 1050 \'mü\'m. Higher spot diameters improved mass removal and minimized repeatability drawbacks. It was observed that the coefficients of variation (CV) of site-to-site measurements decreased by using higher laser focusing diameters. By fixing the laser spot diameter at 750 \'mü\'m, the CV of measurements improved at least 2-fold for all analytes when 50 J cm-2 was applied in comparison to 20 J cm-2. These results can be attributed to a larger mass removal obtained at higher laser fluences and better laser sampling representativeness. Sensitivity did also increase with laser fluence but no significant differences were observed in the detection limits using 25 and 50 J cm-2. Although emission intensities increased with laser fluence the background emission and noise increased as well. On the other hand, particle size distribution of powdered samples affects the atomization and excitation efficiencies by laser induced plasmas. When larger particles are incompletely vaporized the resulting emission signals were lower than those obtained from smaller particles. In this work, significant improvements on emission intensities and CV of measurements were observed when pellets made with particles < 75 \'mü\'m were analyzed. No significant differences were observed (emission intensities and CV of measurements) in the analysis of pellets prepared with particles in the 20-75 \'mü\'m range. Pellets prepared with particles > 75 \'mü\'m presented cohesion drawbacks and resulted non uniform craters after laser ablation. The CV of measurements for most analytes in these materials was > 15 %. Therefore, similar particle size distribution between calibration and test samples is recommended to avoid physical matrix effects on laser-sample interaction

Orientador: Celio Pasquini / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T16:25:47Z (GMT). No. of bitstreams: 1 Cortez_Juliana_D.pdf: 25144768 bytes, checksum: bb2f3753af786e01a3f99e0a7e89fe95 (MD5) Previous issue date: 2012 / Resumo: A técnica de ring oven, originalmente desenvolvida por Weisz em 1954 e revisitada com o objetivo de ser utilizada em um procedimento simples e altamente eficiente de pré-concentração de analitos antes da determinação por técnicas analíticas de microanálise. A técnica de pré-concentração proposta e baseada na utilização de um pequeno volume de amostra que e transferida gota-a-gota, com o auxílio de um sistema de análise por injeção em fluxo, para um substrato de papel de filtro. O papel de filtro e mantido em um pequeno forno circular aquecido (ring oven). As gotas da solução da amostra difundem por capilaridade do centro do papel de filtro para a frente do solvente. Depois do término do processo, um anel com um contorno circular bem definido (0,35 mm de largura e cerca de 2,0 cm de diâmetro) e formado no papel de filtro e este contém, pré-concentrados, os elementos presentes no volume processado de amostra. Coeficientes de preconcentração do analito podem alcancar 250 vezes (m/ m) para um volume de amostra de 600 mL. O sistema proposto foi avaliado para pré-concentrar Na, Fe e Cu presentes em amostras de etanol hidratado combustível, em nível de mg mL. O procedimento de pré-concentração não utiliza nenhum solvente adicional, aos já existentes na amostra, nem reagentes adicionais, podendo ser considerado um método limpo, de acordo com os preceitos da química analítica verde. A determinação direta e simultânea dessas espécies, no contorno do anel, foi realizada empregando a técnica microanalítica de espectroscopia de emissão óptica em plasma induzida por laser (LIBS). Os limites de detecção encontrados atendem as exigências da Agencia Nacional de Petroleo (ANP) para controle do etanol combustível. Os limites de detecção são de 0,9; 0,5 e 0,4 mg kg para sódio, ferro e cobre, respectivamente. O potencial da associação da técnica de ring oven e LIBS, uma representante das técnicas analíticas de microanálise, foi demonstrado, ajudando os limites de detecção das medidas LIBS e abrindo um novo caminho para o uso do ring oven em novas propostas analíticas e na associação com outras técnicas de microanálise / Abstract: The ring oven technique, originally developed by Weisz in 1954, is revisited to be used in a simple though highly efficient procedure for analyte preconcentration prior its determination by the micro-analytical techniques presently available. The proposed preconcentration technique is based on the dropwise delivery of a small volume of sample to a filter paper substrate, assisted by a flow-injection system. The filter paper is maintained in a small circular heated oven (the ring oven). Drops of the sample solution diffuse by capillarity from the center of filter paper to the solvent front. After the total sample volume has been delivered, a ring with a sharp (c.a. 0.35 mm) circular contour, of about 2.0 cm diameter is formed on the paper to contain most of the analytes originally present in the sample volume. Preconcentration coefficients of the analyte can reach 250 fold (on a m/m basis) for a sample volume small as 600 mL. The proposed system and procedure have been evaluated to concentrate Na, Fe and Cu in levels of mg mL in fuel ethanol. The preconcentation procedure uses no solvent or reactant, besides the already existing in the sample, in agreement with the principles of green analytical chemistry. The simultaneous determination of these species in the ring contour, was made by employing the micro-analytical technique of laser induced breakdown spectroscopy (LIBS). The detection limits are sufficient to attend to the requirements of the National Agency of Petroleum (ANP) aiming at the quality control of fuel ethanol. The detection limits are 0.9, 0.5 and 0.4 mg kg for sodium, iron and copper, respectively. The potential of association between the ring oven technique and LIBS, representative of the microanalytical techniques, was demonstrated, helping to achieved a better detectivity in LIBS measurements and opening the path for new analytical proposals and for the association with others microanalytical techniques / Doutorado / Quimica Analitica / Doutora em Ciências

Les déchets solides générés par notre société sont nombreux. Les cendres volantes sont des déchets solides produits lors de la combustion de déchets domestiques ou industriels dans des incinérateurs. Les cendres volantes sont également produites par la combustion du charbon dans les centrales à charbon. Les cendres volantes sont des résultats de ces combustions et représentent importante quantité de déchets produits chaque année par notre société. Les possibilités de recyclage de ces déchets sont nombreuses : dans la construction, l'industrie routière. Elles sont également stockées pour une utilisation ultérieure. Les origines différentes des charbons et déchets incinérés conduisent à une minéralogie et une composition élémentaire complexe. En tant que sous-produit le devenir des cendres volantes est important à déterminer, aussi la détermination de la composition élémentaire de ces cendres volantes est-elle indispensable.Les méthodes classiques de préparation des échantillons solides sont la minéralisation acide ou la fusion alcaline. Ces procédures prennent du temps et supposent l’utilisation de réactif, de plus la digestion complète n'est pas toujours assurée. Le risque de contamination par les réactifs employés est important au cours de ces méthodes classiques de préparation. Au cours de la dernière décennie, le développement d’analyse directe d'échantillons solides en utilisant des méthodes d'ablation laser a été important en raison de la nécessité de réduire le temps d'analyse et de réduire aussi la consommation de réactifs. Dans ce travail, deux méthodes basées sur l'ablation par laser seront étudiées pour l'analyse des cendres: Laser Induced Breakdown Spectroscopy (LIBS) et Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). La spectrométrie LIBS sera étudiée pour la détermination quantitative des éléments majeurs dans les échantillons de cendres alors que le couplage ablation laser ICP / MS sera employé pour détermination des éléments traces. L'optimisation de la sensibilité et les stratégies d'étalonnage sont les principaux problèmes traités dans ce travail. La préparation des échantillons et l’optimisation ont été effectuées pour déterminer les éléments tels que Al, As, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Pb, Sr, V et Zn par les deux méthodes.Les performances analytiques telles que les limites de détection, justesse ont été obtenus à la suite d'optimisations appropriées des liants et de la sélection de l’étalon interne approprié. En conclusion, l’analyse directe de solides en utilisant les techniques basées sur l’ablation laser développées dans ce travail conduisent à une justesse acceptable pour la détermination des éléments majeurs et traces dans les cendres volantes / Solid waste generated by our society are numerous, fly ashes are produced during the combustion of domestic or industrial waste in incinerators. Fly ashes are also produced through coal combustion in coal fired power plants. Fly ashes are results of these combustions and represent important quantity of waste produced every year by our society. They have variable use – in construction, road industry, or they can be stocked for further use. As they are result of different origin, they have complex mineral and elemental composition. As a by-product or as a recycled product fly ashes fate is important to determine. In this view the determination of the elemental composition of fly ashes is the aim of this work.Conventional methods of sample preparation are acid digestion or alkali fusion. These procedures are time and reagent consuming and complete digestion is not assured. The potential contamination of the reagents employed is important during these classical sample preparation methods. During the past decade, development of direct solid sampling using laser ablation methods was important due to the need of reducing analysis time and also reducing reagent consumption. In this work, two methods based on laser ablation will be studied for fly ash analysis: Laser Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). LIBS will be studied for quantitative determination of major elements in fly ash samples while Laser ablation / ICP MS will be employed for trace element determination.The sensitivity optimization and different calibration strategies are key problems of laser sampling methods. Sample preparation and condition optimisation were performed to determine major, minor and trace elements such as Al, As, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Pb, Sr, V and Zn by both methods – LIBS for major elements and LA-ICP-MS for minor and trace elements.Analytical properties such as detection limits, accuracy and analytical working curves were obtained following suitable optimisation of binders and internal standards. Compromise binder and analytical conditions were selected to determine the elements in fly ash samples.In conclusion, direct solid sampling using laser ablation followed by LIBS or for solid introduction into ICP was found to determine major, minor and trace elements in fly ashes, improving pellets mechanical stability, high samples sensitivity and acceptable accuracy and detection limits.

La LIBS (Laser Induced Breakdown Spectroscopy) est une technique d'analyse élémentaire basée sur l'exploitation du spectre d'émission optique issu de l'ablation laser d'un échantillon. Aujourd'hui, la LIBS ne s'est pas encore imposée comme une technique de choix pour la majorité des applications comme c'est le cas pour les techniques de plasma à couplage inductif. L'une des principales raisons à cela est la difficulté à fournir des mesures quantitatives justes. Il existe donc aujourd'hui une nécessité de mieux comprendre et caractériser les plasmas et les phénomènes issus de l'interaction laser-Matière sur tout type de matériaux pour améliorer les performances de cette technique analytique. Cette interaction laser/matière étant, de plus, spécifique au type de matériau analysé, il est indispensable d'étudier ces effets sur une vaste gamme de matériaux. Deux types d'échantillons ont donc été utilisés pour étudier les plasmas LIBS: des matériaux contenant des terres rares et des matériaux plastiques. Les travaux réalisés sur les terres rares ont permis de sélectionner des raies d'analyse « disponibles », c'est-À-Dire sans interférences spectrales provenant des autres éléments de cette famille et suffisamment sensibles pour réaliser une analyse quantitative. Cette étude a mis en avant le fait que les effets de matrice dus à la quantité de terres rares et à la nature de l'échantillon sont importants. Ces effets de matrice sont propres à chaque élément et à chaque matrice, ils sont donc à prendre en considération pour toute analyse LIBS d'un échantillon contenant plusieurs terres rares. Si l'accumulation d'un grand nombre de terres rares a un effet significatif sur le signal d'un de ces analytes, leurs présences en nombre et quantité limitée (2 à 4) donnent un effet compensable par étalonnage interne. Dans le cadre de l'analyse LIBS des matériaux plastiques, une étude détaillée du signal en utilisant différentes conditions de plasma a été réalisée. L'analyse quantitative s'est portée sur plusieurs éléments dont certains difficiles à exciter comme le brome et le chlore. Grâce à l'utilisation d'une atmosphère contrôlée d'hélium, la détection des halogènes employés comme retardateurs de flamme dans les plastiques, a été possible. Un important effet de matrice a été observé à 266 nm en comparaison avec les résultats obtenus à 532 nm. Cependant, ces différences marquées à 266 nm ont permis la discrimination des quatre familles de polymères étudiées. En présence d'hélium, des différences significatives ont été obtenues pour les rapports C2/He et CN/He. En les traçant l'un en fonction de l'autre, il est ainsi possible de discriminer les différents types de plastiques étudiés / The LIBS (Laser Induced Breakdown Spectroscopy) technique is an elemental analysis technique based on the use of the optical emission spectrum from a sample of laser ablation. Today, LIBS has not emerged as a technique of choice for the majority of applications, as is the case for inductive coupled plasma techniques. One of the main reasons for this is the difficulty in providing accurate quantitative measurements. So there is now a need to better understand and characterize plasmas and phenomena from laser-Matter interaction on all types of materials to improve the performance of this analytical technique. This laser/material interaction is specific to the type of material analyzed, so it is essential to study these effects on a wide range of materials. Two types of samples have been used to study LIBS plasmas: materials containing rare earths and plastics. Work on rare earths were used to select the analytical lines free of spectral interference from other elements of this family and sensitive enough to carry out a quantitative analysis. This study highlighted the fact that the matrix effects due to the amount of rare earth and nature of the sample are important. These matrix effects are unique to each element and matrix, so they are to be considered in all LIBS analysis of a sample containing several rare earths. If the accumulation of a large number of rare earths (i.e 12) has a significant effect on the signal of the analytes, the effect of a limited number (i.e. 2 to 4) could be compensated by use on an internal standard. In the context of the LIBS analysis of plastic materials, a detailed study of the signal using different plasma conditions was performed. The quantitative analysis was focused on several elements, including bromine and chlorine which are difficult to excite. Through the use of a controlled atmosphere of helium, the detection of halogens used as flame retardants in plastics was significantly improved. An important matrix effect was observed at 266 nm in comparison with the results obtained at 532 nm. However, these differences at 266 nm allowed the discrimination of four families of polymers studied. In the presence of helium, significant differences were obtained for the C2 / He and CN / He ratios. This criteria was found to be relevant for the discrimination between the different types of plastics studied

Lorsqu'une impulsion laser est focalisée sur une cible solide immergée dans un liquide, de la matière est vaporisée. La nucléation et la croissance ont lieu dans le liquide et des nanoparticules sont ainsi synthétisées. La méthode est très polyvalente puisqu'une grande variété de matériaux peut être générée. De plus, les nanoparticules sont directement stabilisées dans le solvant. L'ajout d'agent complexant n'est pas nécessaire mais peut tout de même permettre de mieux contrôler la taille des nanoparticules. Cependant, de nombreux processus sont mis en jeu durant la synthèse et l'objectif de ce travail doctoral est de développer la compréhension de ces éléments. Dans la mesure où l'ablation laser déploie une multitude d'´échelle de temps, il a fallu employer différentes méthodes pour élucider ces mécanismes. Pour commencer, je définirai un état de l'art de l'utilisation de l'ablation laser en milieu liquide et nos résultats concernant la synthèse d'aluminium oxyde dopé chrome. Par la suite, je présenterai la spectroscopie des plasmas et les questions sous-jacentes à la notion d'´équilibre dans un plasma moléculaire. Ensuite, je décrirai notre approche atomistique de la nucléation basée sur les techniques de chimie quantique. Enfin, je montrerai l'apport de l'utilisation des méthodes d'ombrographie pour mieux comprendre la thermodynamique du système au temps plus long. Notre étude démontre que la bulle formée suite à l'ablation laser est constituée essentiellement de molécule du solvant dont la quantité n'évolue quasiment pas au cours du temps de vie de la bulle / When a pulsed-laser is focused into a solid target immersed in water, the material is evaporated. Nucleation and growth occur in the liquid and nanoparticles are synthesized. The method can be considered as versatile because one can try to synthesize any kinds of materials. Also, the nanoparticles are directly stabilized by the solvant so there is no need of complexing agents. The nanoparticles are described as ligand-free. However, various processes can occur during the synthesis and the aim of my work is to understand these different components. Since the laser ablation in liquid displays a wide range of timescales, we used numerous methods to address this problem. First, I will present the use of plasma spectroscopy and the questions it raises towards local thermodynamic equilibrium. Then, I will describe our microscopic approach of nucleation based on quantum chemistry techniques. Finally, I will illustrate the advantages of shadowgraphic measurements to reach an hydrodynamic understanding of the system

La conservation du patrimoine constitué par les grottes ornées paléolithiques, fragile car très ancien, est un enjeu capital. Dans ce cadre, une approche taphonomique de l’état de surface des parois est envisagée à travers l’étude des concrétions qui recouvrent les parois de grottes. Ceci est primordial pour la compréhension de leurs mécanismes de genèse et de développement qui s’opèrent à l’échelle d’une grotte, d’une salle, d’une paroi ou d’un panneau orné. En effet, ces concrétions peuvent recouvrir de manière partielle ou totale des peintures ou gravures sous-jacentes. L’étude réalisée ici porte sur la caractérisation multiphysique et la variabilité spatiale de deux types de concrétions calcitiques, le mondmilch et les coralloïdes, qui sont fréquemment retrouvés dans les grottes ornées. Elle a été menée principalement dans une grotte laboratoire, la grotte de Leye, à Marquay (Dordogne, France), dépourvue d’intérêt archéologique et située dans la vallée de la Vézère, l’une des régions les plus riches en grottes ornées de France. La composition chimique et la structure des revêtements calcitiques ont été déterminées par l’utilisation conjointe de méthodes de caractérisation physico-chimique comme la spectroscopie sur plasma induit par laser (LIBS) et la spectroscopie Raman, couplées à des observations morphologiques en microscopies optique et électronique. Les coralloïdes, qui ont été très peu étudiés jusqu’à aujourd’hui, ont fait l’objet d’une attention particulière. La mise en perspective des résultats des analyses physico-chimiques portant sur les concrétions, avec d’une part des données concernant l’environnement souterrain telles que le comportement climatique et hydrologique de la cavité, la présence de micro-organismes, et d’autre part des données relatives à l’isotopie et à la datation de la calcite, permet de discuter les hypothèses de formation des faciès. Enfin, l’analyse statistique d’une base de données de cavités constituée à l’échelle de la vallée de la Vézère contribue à alimenter la réflexion sur les paramètres corrélés à la présence des concrétions. / Paleolithic ornated cave conservation is an issue of major interest for curators who are facing several kinds of alterations. The study of speleothems covering cave walls is crucial to have a better understanding of their formation processes at the scale of a cave, a wall, or a panel. They can indeed, partially or totally, cover paintings and engravings. The present work focuses on the physicochemical characterization and spatial variability of two calcitic concretions, moonmilk and coralloids, that are frequently found in prehistoric caves. This study was conducted in a laboratory-cave called the Leye cave (Marquay, France), a cavity affected by these two types of concretions, but without archeological art and located in the Vézère valley (Dordogne, France), a region with a high density of prehistoric caves. Chemical composition and internal structure of these concretions were obtained by combining physicochemical characterization methods like Raman spectroscopy and Laser Induced Breakdown Spectroscopy (LIBS) coupled with morphological observations. We pay particular attention to coralloids, which were far less studied than moonmilk up to now. Environmental conditions such as climatology and hydrology of the cave, as well as the presence of microbial activity are taken into account in order to interpret the results. Putting these results in perspective with dating and isotopic data allows to discuss different assumptions regarding the formation scenario of these concretions. Finally, a statistical analysis on a database of caves established at the scale of the Vézère valley provides information regarding the correlation between some particular parameters and the presence of the concretions.

Le contrôle des procédés représente un enjeu majeur pour les industries chimiques et pétrochimiques afin de garantir la qualité des produits, le contrôle des coûts, le maintien de la productivité et la maîtrise des risques. L'analyse menée directement au coeur des procédés constitue la voie la plus efficace. Cependant, dans la majorité des applications, les analyses élémentaires sont réalisées essentiellement en laboratoire et très rarement en ligne, par la mise en oeuvre de différentes technologies, le plus souvent lourdes et onéreuses. Ce travail de thèse s'inscrit dans le cadre d'un grand projet d'innovation qui couvre le champ de l'analyse élémentaire en ligne, domaine actuellement peu étudié. La technique d'analyse retenue est la spectrométrie LIBS en raison de sa rapidité et de son application à tout état de la matière sans préparation d'échantillon, ce qui lui offre un fort potentiel pour l'analyse en ligne. Cette technique est investiguée afin de réaliser des analyses en ligne d'éléments présents dans des matrices liquides : saumures, huiles silicone et produits pétroliers. L'optimisation des différents paramètres de mesure est réalisée et une approche d'optimisation s'appuyant sur un plan d'expériences est proposée. Différents modes d'échantillonnage de liquide et plusieurs montages LIBS sont étudiés afin de répondre aux problématiques évoquées. Enfin, une transposition au monde industriel est présentée avec le suivi du soufre en ligne dans des produits pétroliers sur un pilote industriel. Les résultats sont encourageants, mais la stabilité perfectible des mesures dans le temps implique d'explorer de nouvelles pistes d'amélioration / Process control is a major challenge for chemical and petrochemical industries so as to ensure product quality, cost control, sustainable productivity and risk management. To do so, carrying out the analysis directly at the core of the process is the most efficient way. However, for most applications, elemental analyzes are mainly performed in the laboratory and rarely on-line, which requires the implementation of different technologies, usually complex and expensive. This work is part of a large innovative project that covers the field of on-line elemental analysis, a research area still understudied to this day. The analytical technique selected here is the Laser Induced Breakdown Spectroscopy. Indeed, its speed and its capability to analyze all states of matter without sample preparation, gives it a great potential for on-line analysis. This technique is investigated in order to achieve on-line analysis of elements contained in various liquid matrices: brines, silicone oils and petroleum products. The optimization of different measurement parameters is performed, including an experimental design based approach. Different liquid sampling configurations and several LIBS setups are designed in order to tackle the issues encountered. Finally, a transposition to the industrial world is presented through on-line monitoring of sulfur in petroleum products on an industrial pilot process. The results are promising, but improving the stability of measurements over time still requires further research

Die in dieser Arbeit vorgestellten Studien untersuchen verschiedene Ansätze für die Analyse von spektroskopischen Daten für die Erforschung anderer Himmelskörper. Der Fokus lag hierbei auf der laserinduzierten Plasmaspektroskopie (LIBS, engl. laser-induced breakdown spectroscopy), aber auch Daten der Raman-Spektroskopie wurden analysiert. Das erste extraterrestrisch eingesetzte LIBS Instrument, ChemCam, auf dem Mars Science Laboratory (MSL) der NASA untersucht die Marsoberfläche seit 2012 und weitere Missionen mit LIBS und Raman Instrumenten zum Mars sind geplant. Neben analytischen Ansätzen wurden statistische Methoden, die als multivariate Datenanalysen (MVA) bekannt sind, verwendet und evaluiert. In dieser Arbeit werden insgesamt vier Studien vorgestellt. In der ersten Studie wurde die Normalisierung von LIBS Daten mit Plasmaparametern, also der Plasmatemperatur und der Elektronendichte, untersucht. In der zweiten Studie wurden LIBS Messungen unter Vakuumbedingungen im Hinblick auf den Ionisierungsgrad des Plasmas untersucht. In der dritten Studie wurden MVA Methoden wie die Hauptkomponentenanalyse (PCA) und die partielle Regression kleinster Quadrate (PLS-R) zur Identifizierung und Quantifizierung von Halogenen mittels molekularer Emissionen angewandt. Die Ergebnisse sind vielversprechend, da es möglich war z.B. Chlor in einem ausgewählten Konzentrationsbereich zu quantifizieren. In der letzten Studie wurden LIBS-Daten mit komplementären Raman-Daten von Mars relevanten Salzen in einem low-level Datenfusionsansatz kombiniert. Es wurden MVA Methoden angewandt und auch Konzepte der high-level Datenfusion implementiert. Mit der low-level LIBS und Raman Datenfusion konnten im Vergleich zu den einzelnen Techniken mehr Salze richtig identifiziert werden. Der Gewinn durch die low-level Datenfusion ist jedoch vergleichsweise gering und für konkrete Missionen müssen individuelle und angepasste Strategien für die gemeinsame Analyse von LIBS und Raman-Daten gefunden werden. / The studies presented in this thesis investigate different data analysis approaches for mainly laser-induced breakdown spectroscopy (LIBS) and also Raman data in the context of planetary in-situ exploration. Most studies were motivated by Mars exploration due to the first extraterrestrially employed LIBS instrument ChemCam on NASA's Mars Science Laboratory (MSL) and further planned LIBS and Raman instruments on upcoming missions to Mars. Next to analytical approaches, statistical methods known as multivariate data analysis (MVA) were applied and evaluated. In this thesis, four studies are presented in which LIBS and Raman data analysis strategies are evaluated. In the first study, LIBS data normalization with plasma parameters, namely the plasma temperature and the electron density, was studied. In the second study, LIBS measurements in vacuum conditions were investigated with a focus on the degree of ionization of the LIBS plasma. In the third study, the capability of MVA methods such as principal component analysis (PCA) and partial least squares regression (PLS-R) for the identification and quantification of halogens by means of molecular emissions was tested. The outcomes are promising, as it was possible to distinguish apatites and to quantify chlorine in a particular concentration range. In the fourth and last study, LIBS data was combined with complementary Raman data in a low-level data fusion approach using MVA methods. Also, concepts of high-level data fusion were implemented. Low-level LIBS and Raman data fusion can improve identification capabilities in comparison to the single datasets. However, the improvement is comparatively small regarding the higher amount of information in the low-level fused data and dedicated strategies for the joint analysis of LIBS and Raman data have to be found for particular scientific objectives.

Wegen der zunehmenden Menge an LIBS-Daten von der Marsoberfläche sowie deren speziellen Herausforderungen bei der Analyse untersucht diese Arbeit, wie die Modellierung und Simulation von solchen LIBS-Spektren genutzt werden kann. Das Ziel ist es, Einblicke in die Eigenschaften von LIBS-Plasmen auf dem Mars zu erhalten und Modelle zu entwickeln, die bei der Analyse von realen Missionsdaten helfen können. Die Modellierung basiert sich auf einem stationären Plasma im lokalen thermischen Gleichgewicht (LTE). Das Plasma wird dabei in eine Reihe homogener Zonen unterteilt und Spektren werden mit dem Strahlungstransfer entlang einer eindimensionalen Sichtlinie durch diese Plasmazonen simuliert. Die Ergebnisse dieser Arbeit zeigen, dass auf LTE basierende Modelle gut auf LIBS-Spektren angewendet werden können, die unter Marsbedingungen gemessen wurden. Für zeitaufgelöste Daten kann die Anpassung eines Zwei-Zonen-Modells verwendet werden, um Einblicke in das Plasma zu erhalten und um die Elementkonzentrationen mit einer höheren Genauigkeit zu bestimmen, als es mit der Saha-Boltzmann-Methode möglich wäre. Allerdings sollten Nicht-Gleichgewichtseffekte in den frühesten und spätesten Phasen der Plasmalebensdauer berücksichtigt werden. Für zeitlich integrierte Spektren, wie sie bei aktuellen Marsmissionen gemessen werden, sind Anpassungen durch ein Zwei-Zonen-Modell aufgrund von zu langen Rechenzeiten nicht durchführbar. Stattdessen kann durch die Methode der spektralen Entmischung eine Überlagerung von Spektren unterschiedlicher Temperaturen und Dichten verwendet werden. Diese Methode ermöglicht keine direkten quantitativen Bestimmungen der Elementkonzentrationen, ist aber ein hervorragendes Werkzeug, um einen Überblick über die große Menge an Informationen zu erhalten, die in den Spektren enthalten sind. / Motivated by existing challenges in analysing LIBS spectra and the increasing quantity of Martian LIBS data, this thesis investigates the modelling and simulation of LIBS spectra for the application to LIBS data in Martian atmospheric conditions. This is done with the aim of providing insights into the characteristics of Martian LIBS plasmas as well as developing tools to assist the analysis of real mission data. The modelling of LIBS spectra is based on a stationary plasma in local thermal equilibrium (LTE). The plasma is then divided into a series of homogeneous zones and spectra are simulated using radiative transfer along a one-dimensional line-of-sight through the plasma zones. The results of this thesis show that spectral modelling based on LTE can be well applied to LIBS data in Martian atmospheric conditions. For time-resolved data, fits of a two-zone plasma model can be used to obtain insights into the plasma as well as improved concentration estimates compared to the Saha-Boltzmann plot method. However, attention to non-equilibrium effects should be given at the earliest and latest stages of the plasma lifetime. For time-integrated spectra, i.e. real mission data, fits of the two-zone model are not feasible due to too long computation times. Instead, a superposition of spectra of different temperatures and densities, i.e. the spectral unmixing method, can be used. Although not directly allowing for quantitative concentration estimates, the method is a great tool to overview the large amount of information contained in the spectra.

Improvements in printing technology have exacerbated the problem of document counterfeiting, prompting the need for analytical techniques that better characterize inks for forensic analysis. In this study, 319 printing inks (toner, inkjet, offset, and intaglio) were analyzed directly on the paper substrate using Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS) and Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS). As anticipated, the high sensitivity of LA-ICP-MS resulted in excellent discrimination (> 99%) between ink samples originating from different sources. Moreover, LA-ICP-MS provided ≥ 90% correct association for ink samples originating from the same source. SEM-EDS resulted in good discrimination for toner and intaglio inks (> 97%) and excellent correct association (100%) for all four ink types. However, the technique showed limited utility for the discrimination of inkjet and offset inks. A searchable ink database, the Forensic Ink Analysis and Comparison System (FIACS), was developed in order to provide a tool that allows the analyst to compare a questioned ink sample to a reference population. The FIACS database provided a correct classification rate of 94-100% for LA-ICP-MS and 67-100% for SEM-EDS. An important consideration in forensic chemistry is the interpretation of the evidence. Typically, a match criterion is used to compare the known and questioned sample. However, this approach suffers from several disadvantages, which can be overcome with an alternative approach: the likelihood ratio (LR). Two LA-ICP-MS glass databases were used to evaluate the performance of the LR: a vehicle windshield database (420 samples) and a casework database (385 samples). Compared to the match criterion, the likelihood ratio led to improved false exclusion rates (< 1.5%) and similar false inclusion rates (< 1.0%). In addition, the LR limited the magnitude of the misleading evidence, providing only weak support for the incorrect proposition. The likelihood ratio was also tested through an inter-laboratory study including 10 LA-ICP-MS participants. Good correct association rates (94-100%) were obtained for same-source samples for all three inter-laboratory exercises. Moreover, the LR showed a strong support for an association. Finally, all different-source samples were correctly excluded with the LR, resulting in no false inclusions.