Die Analyse von organischen Polymeren mittels Massenspektrometrie mit induktiv gekoppeltem Plasma nach Laserablation unterliegt starken Matrixeffekten. Mögliche Korrekturmodelle sollten basierend auf der tatsächlich ablatierten Elementmasse sowie der Signalintensität des Kohlenstoffisotops C-13 (13C-Korrektur) entworfen werden. Damit die 13C-Korrektur erfolgreich verlaufen kann, ist ein direkter Zusammenhang zwischen ablatiertem Kohlenstoff und gemessenem 13C-ICP-MS Signal erforderlich. Dies wurde überprüft, indem unter Anwendung der konfokalen Mikroskopie das Ablationskratervolumen bestimmt und der ablatierte Kohlenstoff berechnet wurde. Dieser Zusammenhang konnte sowohl für undotierte, wie auch für elementdotierte Polymere und die Verwendung verschiedener Ablationsgase (Helium, Argon und Sauerstoff) ermittelt werden. Eigens hergestellte polymere elementdotierte Standardmaterialien wurden hinsichtlich der Matrixeffekte charakterisiert. Als größter Einflussfaktor stellte sich die unterschiedliche Ablationsrate bei der Ablation verschiedener Polymere heraus. Unter Anwendung der tatsächlich ablatierten Elementmasse sowie unter Anwendung der 13C-Korrektur konnte die Matrixabhängigkeit deutlich verringert werden.

L’accident de la centrale de Fukushima Dai-ichi en 2011 a conduit au dépôt d’ultra-traces d’uranium et de plutonium sur les sols des bassins versants côtiers du nord-est du Japon, s’ajoutant à l’uranium naturel et au plutonium issu des retombées globales des essais nucléaires atmosphériques, déjà présents avant l’accident. La contribution relative de ces différentes sources peut être quantifiée à partir de la mesure précise de leur composition isotopique et à la détermination précise des signatures isotopiques locales antérieures à l’accident grâce aux données bibliographiques et à l’analyse d’une carotte sédimentaire prélevée dans un réservoir de barrage. Ainsi, l’analyse d’échantillons de sols prélevés après 2011 montre que la distribution spatiale des dépôts initiaux de plutonium est globalement similaire à celle du radiocésium. De plus, si le marquage en uranium de la centrale n’a pas été observé, le plutonium issu de l’accident a été mis en évidence et quantifié dans tous les sédiments (de rivières) analysés, démontrant que le plutonium provenant de la centrale est plus rapidement exporté vers l’Océan Pacifique que celui qui provient des essais atmosphériques. Par ailleurs, des microparticules portant le plutonium ont été localisées puis caractérisées précisément (taille, morphologie, composition chimique). De manière générale, ces travaux ont fourni des données originales sur le devenir des actinides dans l’environnement de Fukushima. / The 2011 Fukushima Dai-ichi accident led to the deposition of uranium and plutonium at ultra-trace levels on coastal catchments in northeastern Japan, in addition to the natural uranium and plutonium from the global fallout of the atmospheric nuclear tests, already present before the accident. The relative contribution of these different sources can be quantified from the precise measurement of their isotopic composition and the precise determination of local isotopic signatures prior to the accident through the compilation of literature data and the analysis of a sediment core collected in a dam reservoir. Furthermore, the analysis of soil samples collected after 2011 shows that the spatial distribution of initial plutonium deposits is roughly similar to that of radiocaesium. In addition, if the presence of uranium originating from the plant was not confirmed, the plutonium rejected by the accident was identified and quantified in all the river sediment samples analyzed, showing that the plutonium originating from the plant is more quickly exported to the Pacific Ocean than that originating from the global atmospheric tests. In addition, plutonium bearing micro particles were localized and then precisely characterized (size, morphology, chemical composition). Overall, this work provided original data on the fate of actinides in the Fukushima environment.

[pt] A distribuição de elementos de terras raras (REE) é representativa das rochas e solos que originalmente os contêm e é frequentemente usada como parâmetro geoquímico ou ambiental para identificação de fontes. Este trabalho propõe um novo método de preparo de amostras para a determinação de elementos de terras raras (REE) por espectrometria de massa de plasma acoplada indutivamente (ICPMS) em amostras ambientais com altas concentrações de Ba. O método consiste na diluição das amostras, obtidas após decomposição ácida em sistema aberto, com ácido sulfúrico 10 porcento (v/v) para a separação de Ba2positive como BaSO4. A remoção da interferência sobre os isótopos de Eu (151Eu and 153Eu) foi eficiente para concentrações de Ba superiores a 0,1 mg L-1. A exatidão e a precisão foram verificadas pela análise de tres materiais certificados, rocha basáltica (NIST 688), Geological Survey (Granite G-2) e sedimento marinho (MESS-3). A metodologia proposta foi aplicada ao pavimento asfáltico, à brita e ao material de referencia certificado. Adicionalmente, todas as amostras foram decompostas por fusão alcalina e as concentrações de elementos majoritários e Eu foram determinadas por espectrometria de emissão ótica de plasma acoplada indutivamente (ICP OES). Os resultados da Eu estavam de acordo com a metodologia proposta, e os limites de detecção (LOD) para REE variaram de 0,003 mg L-1 (Lu) a 0,010 mg L-1 (Gd). A distribuição de REE foi medida em sedimentos superficiais e amostras de testemunhos coletados na Baía de Sepetiba, entre junho e setembro de 2016. A faixa de concentração de SREE foi entre 25-496 mg kg-1. Esse monitoramento é importante para avaliar o impacto da urbanização e desenvolvimento rápido e não planejado de atividades antropogênicas, comuns em muitas áreas costeiras tropicais do Brasil. / [en] The distribution of rare earth elements (REE) is representative of the rocks and soils that originally contain them and it is often used as a geochemical or an environmental parameter for source identification. This thesis proposes a new method for the determination of rare earth elements (REE), by inductively coupled plasma mass spectrometry (ICP-MS), in challenging environmental samples with high Ba concentrations. The method consists in diluting the wet sample digests, obtained after acid decomposition in an open system, with 10 porcento (v/v) sulfuric acid for the separation of Ba2+ as BaSO4. The interference removal on both Eu isotopes (151Eu and 153Eu) was efficient for Ba concentrations higher than 0.1 mg L-1. Accuracy and precision were verified by analysis of two certified materials, NIST 688 Standard Reference Material of basalt rock, Geological Survey G-2 granite and marine sediment reference material (MESS-3) provided by the National Research Council in Canada (NRC) was used to evaluate the accuracy of the REE determination in marine sediments. The proposed methodology was applied to asphalt pavement and crushed stone. Additionally, for comparison, all samples were decomposed by fusion and major elements and Eu concentrations were determined by inductively coupled plasma optical emission spectrometry (ICP OES). The Eu results were in agreement with the proposed methodology, and limits of detection (LOD) for REE varied from 0.003 mg L-1 (Lu) to 0.010 mg L-1 (Gd). The distribution of REE was also measured in surface sediments and sediment core collected in Sepetiba Bay, between June and September of 2016. The range of SREE concentrations was established between 25-496 mg kg-1. This monitoring is important to evaluate the impact of the fast and unplanned urbanization and development of anthropogenic activities, common to many tropical coastal areas in Brazil.

Les nanoparticules d’argent (Ag NPs) sont considérablement utilisées dans l’industrie alimentaire. Elles sont fortement appliquées comme enrobages d’emballages alimentaires afin d’assurer une meilleure qualité des aliments et une plus longue durée de conservation sur les étagères des supermarchés. En revanche, les risques associés aux Ag NPs sont inquiétants. Leurs effets potentiels sur les humains et sur l’environnement suscitent un grand intérêt scientifique. C’est pourquoi il est important de valider des méthodes analytiques pour détecter, caractériser et quantifier les Ag NPs dans la nourriture mise en contact avec ce type de contenant. Les méthodes permettront de mieux comprendre la migration de l'argent vers les aliments directement ingérés par l’humain. La spectrométrie de masse à plasma à couplage inductif en mode particule unique (SP-ICP-MS) est une technique prometteuse pour caractériser et quantifier de petites particules (de quelques nanomètres) à de faibles concentrations (dans l'ordre du ng L-1). Contrairement aux techniques analytiques conventionnelles, telles que les techniques de microscopie et de diffusion de la lumière, le SP-ICP-MS distingue la forme ionique de la forme particulaire de l'analyte. Cette présente étude valide une méthode pour la caractérisation et la quantification des Ag NPs et de l’argent ionique dans deux boissons et trois simulants: jus d'orange, préparation en poudre pour nourrissons, eau Milli-Q, acide acétique à 3% et éthanol à 10%. De plus, une meilleure compréhension du devenir et de la migration de l’argent provenant d'emballages alimentaires nano-activés a pu être obtenue. En effet, les milieux acides et les traitements thermiques ont engendré de plus grands relargages d’argent, sous forme ionique, contrairement aux milieux dits « lipophiles » tels que la préparation pour nourrissons et l’éthanol. En conclusion, ce mémoire nous démontre que les voies de libération des NPs des contenants nano-activés ne sont pas encore très bien comprises. De plus amples études doivent être entreprises afin de pouvoir établir des modèles de migration clairs et afin de mieux comprendre les risques associés à leurs utilisations. / Silver nanoparticles (Ag NPs) are increasingly used in the food industry. They are integrated into coatings of various food packaging to help ensure longer product shelf life. However, the risks associated with Ag NPs are currently not well known and their potential effects on humans are causing growing concern. Furthermore, it is not clear whether NPs have greater or lesser risk than dissolved silver ions or bulk phase Ag. Consequently, it is necessary to detect and to characterize the release of silver from silver-enhanced containers into real food matrices using sensitive analytical techniques that allow one to distinguish between silver ions and nanoparticles. Single particle ICP-MS is a promising technique to count and size small particles at low concentrations. Compared to other conventional instrumentation, it can distinguish between ionic and particulate forms of the analyte. This thesis focused firstly on the validation of an analytical method for the analysis of Ag NPs and ionic silver in three different food simulants (Milli-Q water, 10% ethanol and 3% acetic acid) and in two drinks (orange juice and infant milk formula). A better understanding of the aging and of the migration of silver has been reached in these matrices. Essentially, acidic media caused significant NP oxidation whereas organic macromolecules like lipids, proteins and polysaccharides appeared to increase the stability of the NPs. Subsequently, a migration study from silver-enhanced containers showed significant release of dissolved Ag in 3% acetic acid and a lower release in milk formula. Also, heating led to a considerable release of silver from the container. To conclude, further studies are needed to obtain clear release models to better understand the risk on humans and on the environment.

[pt] Os metais estão presentes em diversos materiais e muitos deles, como o níquel e o cromo, possuem papeis significativos em diversos setores industriais. A quantificação desses metais é importante tanto para obtenção de informações relevantes a respeito desses materiais, como para avaliação de possíveis contaminações ambientais. No presente trabalho, foram desenvolvidos métodos analíticos para a determinação de níquel e cromo em amostras de asfalto, brita e CAP por espectrometria de massa com plasma indutivamente acoplado usando calibração externa e diluição isotópica. Para a avaliação da exatidão dos métodos foram utilizados os materiais de referência certificados NIST 1084a e NBS 688. Como métodos de preparo de amostra, foram estudadas a decomposição ácida em bloco digestor, e a diluição em uma mistura de xileno/butanol na proporção 60:40 v:v (para amostras de óleo). Para a correção da interferência da espécie 40Ar12C positivo sobre o isótopo de 52Cr foi utilizada a célula de reação dinâmica com introdução de CH4 como gás de reação, o que reduziu de forma significativa o sinal de fundo característico para o isótopo de cromo. Os métodos desenvolvidos se mostraram eficientes na determinação dos metais. As recuperações obtidas para os SRMs se encontram entre 80-120 porcento. As concentrações médias, em mg kg-1 , encontradas para Ni pelos diferentes métodos nas amostras de CAP, brita e asfalto foram, respectivamente 39,9 mais ou menos 0,6, 6,7 mais ou menos 0,5 e 11,2 mais ou menos 0,8, enquanto para Cr as concentrações foram 1,8 mais ou menos 0,1, 15,3 mais ou menos 0,3, 16,6 mais ou menos 0,4. O sucesso da aplicação da diluição isotópica em amostras dissolvidas em solvente orgânico mostrou-se muito promissor, pois elimina a necessidade da decomposição ácida das matrizes tornando o preparo das amostras mais rápido e menos trabalhoso. / [en] Metals are present in several samples and many of them, such as nickel and chromium, have significant roles in several industry sectors. The quantification of these metals is important both for obtaining relevant information regarding these materials, and for evaluating possible environmental contaminations. In the present work, analytical methods were developed for the determination of nickel and chromium in asphalt, crushed stone and CAP samples by inductively coupled plasma mass spectrometry using both external calibration technique and isotopic dilution. To evaluate accuracy of the method, the certified reference materials NIST 1084a and NBS 688 were used. Two different methods of sample preparation were employed, block digestion and direct dilution in a xylene / butanol mixture using a 60:40 v:v ratio (for the oil samples). For the interference correction imposed by 40Ar12C over 52Cr, the dynamic reaction cell was used with CH4 as the reaction gas, which significantly reduced the characteristic background signal of the chromium isotope. The methods developed proved to be efficient in the determination of the metals in question. The recovery values obtained for the SRMs were between 80-120 percent. The average concentrations, in mg kg-1 , found for Ni by the different methods in CAP, crushed stone and asphalt samples were, respectively, 39,9 more or less 0,6, 6,7 more or less 0,5 and 11,2 more or less 0,8, while for Cr the concentrations were 1,8 more or less 0,1, 15,3 more or less 0,3, 16,6 more or less 0,4. The successful application of isotope dilution in samples dissolved in organic solvent is very promising because it eliminates the need for acid digestion, making the sample preparation faster and less labor intensive.

[pt] Tinturas de cabelo, amplamente utilizadas em cosméticos, demandam atenção especial para garantir a ausência de substâncias prejudiciais à saúde. A Agência Nacional de Vigilância Sanitária (ANVISA) estabelece limites de impurezas, como 20 mg kg(-1) para Pb e 100 mg kg(-1) para a soma dos demais elementos potencialmente tóxicos. A fim de avaliar a ocorrência de elementos potencialmente tóxicos em tinturas comercializadas no Brasil, a espectrometria de massa com plasma indutivamente acoplado (ICP-MS) foi empregada neste estudo para determinar as concentrações de Al, Ba, Be, Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, Pb, Sb, Sn, Sr, Ti e Zn em 26 amostras de tinturas de cabelo. A maioria das amostras apresentou baixas concentrações dos elementos estudados (< 1 mg kg(-1) ), exceto Pb em duas amostras (T01 e T09), tinturas à base de acetato de chumbo, que apresentaram concentrações de até 3.500 mg kg(-1) , e Al com concentrações de até 480 mg kg(-1) para a amostra H01. Utilizando metodologia do Scientific Committee on Consumer Safety da União Europeia, foram avaliados os riscos à saúde associados à exposição prolongada a esses elementos. Alguns elementos demonstram margens de segurança (MS) maiores do que 100, indicando exposição segura de acordo com a Environment Protection Agency (EPA). No entanto, Al, Pb, Cr, Mn e Ni apresentaram valores de MS abaixo de 100, suscitando preocupações em relação ao uso prolongado de algumas tinturas comerciais por apresentarem um valor de MS considerado inseguro (MS < 100) pela EPA. / [en] Hair dyes, widely used in cosmetics, require special attention to ensure the absence of harmful substances to health. The Agência Nacional de Vigilância Sanitária (ANVISA) establishes limits for impurities, such as 20 mg kg(-1) for Pb and 100 mg kg(-1) for the sum of other potentially toxic elements. In order to assess the occurrence of potentially toxic elements in hair dyes marketed in Brazil, inductively coupled plasma mass spectrometry (ICP-MS) was employed in this study to determine the concentrations of Al, Ba, Be, Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, Pb, Sb, Sn, Sr, Ti, and Zn in 26 hair dye samples. Most samples showed low concentrations of the studied elements (< 1 mg kg(-1) ), except for Pb in two samples (T01 and T09), lead acetate-based dyes, which showed concentrations of up to 3,500 mg kg(-1) , and Al with concentrations of up to 480 mg kg(-1) for sample H01. Using the methodology of the Scientific Committee on Consumer Safety of the European Union, health risks associated with prolonged exposure to these elements were assessed. Some elements demonstrate margin of safety (MS) greater than 100, indicating safe exposure according to the Environmental Protection Agency (EPA). However, Al, Pb, Cr, Mn, and Ni showed MS values below 100, raising concerns regarding the prolonged use of some commercial dyes as they present a MS value considered unsafe (MS < 100) by the EPA.

The Eagle Ford Shale and equivalent Boquillas Formation (Late Cretaceous) contain abundant volcanic ash beds of varying thickness. These ash beds represent a unique facies that displays a range of sedimentary structures, bed continuity, and diagenetic alteration. They are prominent not only in West Texas outcrops, but also in the subsurface of South Texas where hydrocarbon production is actively occurring. The ash beds have the potential to be used for stratigraphic correlation for understanding early diagenesis and — most importantly — for obtaining high-resolution geochronology, which can then be used for defining depositional rates and chronostratigraphy. Study of the ash beds was conducted at outcrops along U.S. 90, west of Comstock, Texas, the subsurface in Atascosa and Karnes County, and at a construction site in South Austin. Bed thicknesses range from 0.1–33 cm and were collected throughout the entirety of the Eagle Ford succession. Mineral separation yielded abundant non-detrital zircons for U-Pb dating. Dating was conducted using LA-ICP-MS at The University of Texas at Austin, to attain a base level understanding of the age range for the Eagle Ford. High-resolution ages for the base and top of the Eagle Ford were obtained, in addition to radioisotopically defining the Cenomanian-Turonian boundary within the section. U-Pb ages for the Eagle Ford Shale range from Early Cenomanian to Late-Coniacian near Comstock, Mid-Cenomanian to the Turonian-Coniacian boundary in the subsurface, and Early Cenomanian to Late Turonian in Austin area. These findings contrast with many of the regional biostratigraphic studies across the Eagle Ford and indicate a more prolonged period of Eagle Ford deposition than previously observed. / text

Les carbonatites sont des roches magmatiques essentiellement composées de carbonates (calcite et/ou dolomite) d'origine magmatique. Leur statut pétrographique en tant que liquide magmatique ou cumulat reste à l'heure actuelle fort contreversé. Cette thèse de doctorat à pour objectif une étude pétrographique fine de ces roches couplée à des microanalyses in-situ des éléments en trace des principaux minéraux (carbonate, apatite).

Coal is one of the major energy sources in the world and contains most of the elements from the periodic table. During combustion of coal these elements are released and redistributed. This may lead to environmental problems. Some of these elements are considered to be very dangerous for human and animal health and ecosystems. The knowledge of concentration and speciation of elements in coal is important for the prevention of the adverse environmental phenomena associated with the use of coal. One of the hazardous elements in coal is lead. The purpose of this work is to determine the concentration of lead and its isotopic composition simultaneously with determining the speciation of lead in coal. The ICP-MS method was used to determine the concentration and isotope ratios of lead. A total of 62 samples of subbituminous coal was analyzed. The method of selective extraction analysis BCR was used on 9 samples of subbitumnious coal to identify the speciation of lead in coal. Lead concentrations in coal were measured in the range of 0.25 to 78.84 mg·kg-1 . These concentrations correspond to the average concentrations of lead in most of the coals. Isotope ratio 206 Pb/207 Pb in coal samples ranged from 1.169 to 1.219. Isotopic 208 Pb/206 Pb ratio was measured in the interval 2.047 to 2.093. The isotopic...

15 samples of gem opals were analyzed by laser ablation inductively coupled plasma mass spectrometry (LA ICP-MS) and inductively coupled plasma mass spectrometry (ICP-MS). For this study were selected the most representative samples from Slovakia, Australia, Peru, Ethiopia, Mexico, USA and the Czech Republic. These samples were obtained from private collections. The study focuses on the geochemical relationships between various forms of opal originating from igneous and sedimentary environments based on the results from LA ICP-MS and ICP-MS. The major and trace element compositions are unique for each studied opal locality and important for understanding numerous aspects of opal formation. Major element analysis shows that opals are essentially pure SiO2 (77 - 92 wt. %). Al, Fe, Ca, K, Na and Mg are the main elemental impurities. The concentrations of the trace elements vary strongly depending on the opal locality. Differences were found, e.g., in the concentrations of REE and some refractory elements, which might be indicative for determining the provenance of opals. Many studies have been published explaining the origin of luminescence, microstructures and the thermal properties of opals. However, there are very few comprehensive studies comparing gem opals from the most important historical and...