O principal objetivo deste trabalho foi desenvolver uma metodologia de análise de soro sanguíneo utilizando os métodos Proton Induced X-ray Emission (PIXE) e Inductively Coupled Plasma Mass Spectrometry (ICP-MS). O PIXE é um método de análise multielementar baseado na detecção dos raios-X característicos emitidos pelas amostras, quando bombardeadas com feixes de íons (H+, He+, ...) com energia da ordem de alguns MeV. Já o ICP-MS é um espectrômetro de massa que analisa componentes de amostras ionizadas, separados de acordo com suas razões massa carga (m/z). Para a realização deste estudo, as amostras de sangue dos voluntários (30 jovens com idade entre 18 e 25 anos) foram coletadas no Hospital Universitário da USP utilizando tubos de vidro da BD VacutainerTM sem aditivos (Processo do Comitê de Ética: HU-615/05). O soro foi obtido pela centrifugação dos tubos a 3000 rpm. As amostras foram pipetadas sobre Nuclepore (10?m de espessura) e secas a temperatura ambiente, para o método PIXE, e diluídas de 1:10, para as análises com ICP-MS. A acurácia dos resultados foi verificada analisando materiais de referências de soro do National Institute of Public Health - Québec (ICP-03B-02 e ICP-02-S-05). A análise dos padrões apresentou 78% dos dados entre ±1?, 14% entre ±2? e 4% além de ±3?. Este estudo de elementos traço em soro humano revelou um total de 22 elementos: Be, Al, P, S, Cl, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Se, Br, Mo, Cd, Sn, Tl e Pb, com concentrações entre 9 ng/l e 6 g/l, o que compreende 9 ordens de grandeza, e também permitiu o estudo das funções de distribuição de probabilidades dos elementos. As técnicas utilizadas foram eficientes e complementares na realização deste trabalho. Os resultados das concentrações elementares medidas neste trabalho concordaram com os valores da literatura. / The main objective of this work was to develop a methodology for the analysis of blood serum by Proton Induced X-ray Emission (PIXE) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). PIXE is a multi elementary spectrometric method that relies on the detection of characteristics X-rays emitted by a sample bombarded with an energetic (~MeV) ion beam (H+, He+, ...). With the ICP-MS one measures the elementary components in an ionised sample, separated according to their mass to charge ratio (m/z). For this study, the blood samples were collected from 30 young healthy adult volunteers with age between 18 and 25 years, in the University Hospital using additiveless BD VacutainerTM tubes (Authorisation agreement HU-615/05). Blood serum was obtained by centrifugation of the tubes at 3000 rpm. For PIXE analysis, the serum samples were pipetted on Nuclepore film (10?m thick) and dried at room temperature. For the ICP-MS analysis, the serum samples were diluted 1:10. Accuracy of both methods was obtained analysing serum reference materials supplied by the National Institute of Public Health - Québec (ICP-03B-02 and ICP-02-S-05). The analysis of the reference materials presented results for the elementary concentrations within ±1? for 78% of the data, 14% of the data lied within ±1? and ±2?, and 4% above ±3?. The analysis of trace elements in human blood serum by PIXE and ICP-MS revealed a total of 22 elements, ranging over 9 orders of magnitude: Be, Al, P, S, Cl, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Se, Br, Mo, Cd, Sn, Tl e Pb, with concentrations between 9 ng/l and 6 g/l. The PIXE and ICP-MS techniques were efficient and complimentary for the accomplishment of this work. The elementary concentrations measured in this work agreed with overall data in literature.

O principal objetivo deste trabalho foi desenvolver uma metodologia de análise de soro sanguíneo utilizando os métodos Proton Induced X-ray Emission (PIXE) e Inductively Coupled Plasma Mass Spectrometry (ICP-MS). O PIXE é um método de análise multielementar baseado na detecção dos raios-X característicos emitidos pelas amostras, quando bombardeadas com feixes de íons (H+, He+, ...) com energia da ordem de alguns MeV. Já o ICP-MS é um espectrômetro de massa que analisa componentes de amostras ionizadas, separados de acordo com suas razões massa carga (m/z). Para a realização deste estudo, as amostras de sangue dos voluntários (30 jovens com idade entre 18 e 25 anos) foram coletadas no Hospital Universitário da USP utilizando tubos de vidro da BD VacutainerTM sem aditivos (Processo do Comitê de Ética: HU-615/05). O soro foi obtido pela centrifugação dos tubos a 3000 rpm. As amostras foram pipetadas sobre Nuclepore (10?m de espessura) e secas a temperatura ambiente, para o método PIXE, e diluídas de 1:10, para as análises com ICP-MS. A acurácia dos resultados foi verificada analisando materiais de referências de soro do National Institute of Public Health - Québec (ICP-03B-02 e ICP-02-S-05). A análise dos padrões apresentou 78% dos dados entre ±1?, 14% entre ±2? e 4% além de ±3?. Este estudo de elementos traço em soro humano revelou um total de 22 elementos: Be, Al, P, S, Cl, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Se, Br, Mo, Cd, Sn, Tl e Pb, com concentrações entre 9 ng/l e 6 g/l, o que compreende 9 ordens de grandeza, e também permitiu o estudo das funções de distribuição de probabilidades dos elementos. As técnicas utilizadas foram eficientes e complementares na realização deste trabalho. Os resultados das concentrações elementares medidas neste trabalho concordaram com os valores da literatura. / The main objective of this work was to develop a methodology for the analysis of blood serum by Proton Induced X-ray Emission (PIXE) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). PIXE is a multi elementary spectrometric method that relies on the detection of characteristics X-rays emitted by a sample bombarded with an energetic (~MeV) ion beam (H+, He+, ...). With the ICP-MS one measures the elementary components in an ionised sample, separated according to their mass to charge ratio (m/z). For this study, the blood samples were collected from 30 young healthy adult volunteers with age between 18 and 25 years, in the University Hospital using additiveless BD VacutainerTM tubes (Authorisation agreement HU-615/05). Blood serum was obtained by centrifugation of the tubes at 3000 rpm. For PIXE analysis, the serum samples were pipetted on Nuclepore film (10?m thick) and dried at room temperature. For the ICP-MS analysis, the serum samples were diluted 1:10. Accuracy of both methods was obtained analysing serum reference materials supplied by the National Institute of Public Health - Québec (ICP-03B-02 and ICP-02-S-05). The analysis of the reference materials presented results for the elementary concentrations within ±1? for 78% of the data, 14% of the data lied within ±1? and ±2?, and 4% above ±3?. The analysis of trace elements in human blood serum by PIXE and ICP-MS revealed a total of 22 elements, ranging over 9 orders of magnitude: Be, Al, P, S, Cl, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Se, Br, Mo, Cd, Sn, Tl e Pb, with concentrations between 9 ng/l and 6 g/l. The PIXE and ICP-MS techniques were efficient and complimentary for the accomplishment of this work. The elementary concentrations measured in this work agreed with overall data in literature.

O grande magmatismo intracontinental ocorrido a 133 Ma na Bacia do Paraná foi desenvolvido por um sistema fissural no qual a interação da Pluma Tristão da Cunha na base da litosfera (com ou sem contaminação crustal) gerou derrames, diques e sills no Brasil, nos Estados do RS, SC, PR, SP, MT, MS e GO, e em parte do Paraguai, Argentina e Uruguai. Na Formação Serra Geral, representativa deste intenso magmatismo, foram coletadas amostras de sills (RS, PR, SP e GO) cristalizados entre os sedimentos Paleozóicos pré-vulcânicos da Bacia do Paraná. Já haviam sido realizados diversos estudos geoquímicos a partir da década de 80 com objetivo de identificar as variações químicas de diques, derrames e sills da Formação Serra Geral. No entanto, a utilização de novas técnicas analíticas (EPMA e LA-ICP-MS), utilizadas no presente estudo, proporcionaram o entendimento das variações químicas de forma pontual em minerais ígneos. A geoquímica dos sills estudados caracteriza-os como sub-alcalinos toleíticos continentais que variam de basaltos a andesitos basáltico. Assim, podendo ser divididos em dois grupos químicos: sills do Rio Grande do Sul (baixo TiO2 < 2 wt.%, com concentrações inferiores de P2O5, Nb, Sr, Zr, Zn, Y e Pb e concentrações superiores de Rb, Th, U, e Cs) e sills do Paraná, São Paulo e Goiás (alto TiO2 >2 wt.%, de geoquímica oposta). Petrograficamente, os sills do RS possuem granulação mais fina, ocorrência restrita de cobre nativo e distribuição modal elevada para plagioclásios cálcicos, quando comparados ao sills do PR, SP e GO. A determinação geoquímica por micro-análise em plagioclásios e clinopiroxênios demonstra que as variações químicas identificadas em rocha total são relatas as modificações químicas ocorridas nestes minerais. Variações do coeficiente de partição (KD) de elementos traços compatíveis em diversas zonas de cristais de plagioclásio e clinopiroxênio possuem correlação na substituição dos elementos Ca, Na, Al, Fe e Mg nos sistemas NaAlSi3O8-CaAl2Si2O8 e Mg2Si2O6-CaMgSi2O6-CaFeSi2O6- Fe2Si2O6, respectivamente. Coeficientes de partição de cristais de plagioclásio e clinopiroxênio agora são determinados em diferentes porções de núcleo, intermédio e borda aprimorando o conhecimento da variação do KD até então determinado como um único valor apenas para o cristal. / The large intracontinental magmatism occurred at 133 Ma in the Paraná Basin was developed by a fissure system in which the interaction of Tristan da Cunha plume at the base of the lithosphere (with or without crustal contamination) caused lava flows, dikes and sills in the RS, SC, PR, SP, MT, MS and GO and part of Paraguay, Argentina and Uruguay. In the Serra Geral Formation, representative of intense magmatism, sills crystallized samples were collected (RS, PR, SP and GO) between the Paleozoic prevolcanic sediments of Paraná basin. Several geochemical studies have been carried out since the 80's in order to identify the chemical variations of dikes, sills and lava flows of the Serra Geral Formation. However, the use of new analytical techniques (EPMA and LA-ICP-MS) provided the study of chemical variations in a timely manner in igneous minerals. The geochemistry of the sills studied characterized them as sub-alkaline continental tholeiitic basalts ranging from the basalt to basaltic andesites. Divided into two chemical groups: sills of Rio Grande do Sul (low TiO2 <2 wt.%, With lower concentrations of P2O5, Nb, Sr, Zr, Zn, Y and Pb and higher concentrations of Rb, Th, U, and Cs) and sills of Parana, Sao Paulo and Goiás (high TiO2> 2 wt.%, geochemical opposite). Petrographically the sills of the RS have finer grain, restricted occurrence of native copper and modal higher to calcic plagioclase, compared to the sills of the PR, SP and GO. Geochemical determination by micro-analysis in plagioclases and clinopyroxenes show that the chemical variations identified in whole rock we describe the chemical changes occurring in these minerals. Variations of the partition coefficient (KD) of compatible trace elements in various parts of crystals of plagioclase and clinopyroxene were correlated in the replacement of Ca, Na, Al, Fe and Mg systems NaAlSi3O8-CaAl2Si2O8 and Mg2Si2O6-CaMgSi2O6-CaFeSi2O6-Fe2Si2O6, respectively. Partition coefficients of crystals of plagioclase and clinopyroxene are now determined in different portions of core, intermediate and rim enhance knowledge of the variation of KD previously determined as a single value only to the crystal.

New methodologies for the collection and analysis of biological samples from psychological, physical and emotional stress are described. Currently, there is little research relating to the elemental, VOC and small molecule changes in biological samples as a consequence of stress on the human body, with much of the current research indicating physical symptoms. This research sought to measure chemical changes in three different categories of stress. The first uses an existing PASAT intervention to induce psychological stress and a further two new methodologies using exercise to induce physical stress and a trapped human in a simulation of a collapsed building to induce emotion stress. Psychological, physical and emotional stress elemental profiles are compared against their respective chemical baseline profiles. Skin samples are collected from the foreheads of participants who endured emotional stress while drool saliva, urine, plasma and forehead skin samples were obtained from physically stressed participants. Furthermore, drool saliva is also obtained from the individual who experienced emotional stress.

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.

Les monnaies anciennes à base d'argent présentent fréquemment des variations de composition en fonction de la profondeur qui apparaissent principalement suite à leur enfouissement. Une analyse juste de ces échantillons impose de s'affranchir de cette couche superficielle perturbée pour caractériser l'alliage qui n'a pas été affecté par ces modifications. L'analyse par spectrométrie de masse couplée à un plasma inductif avec prélèvement par ablation laser (LA-ICP-MS) permet une approche en profils de concentration qui peut rendre compte des variations de teneur selon la profondeur. Un protocole analytique par LA-ICP-MS a été développé spécifiquement pour les monnaies d'argent, qui permet de visualiser la couche de surface perturbée pour caractériser l'alliage sain lors de l'analyse des éléments majeurs. Les caractéristiques intrinsèques de la méthode LA-ICP-MS ont bénéficié au dosage des éléments mineurs et traces : le nombre d'éléments dosés et les limites de détection très basses permettent de caractériser l'ensemble des constituants de ces alliages. Des méthodes d'analyse complémentaires ont été mises en œuvre pour valider le protocole analytique proposé. <br />Les monnaies d'argent des premiers souverains carolingiens sont les premières à avoir bénéficié des avancées analytiques permises par l'application de la méthode LA-ICP-MS aux échantillons de ce type. L'évolution du titre d'argent de pièces frappées entre 751 et 864 a été étudiée, et corrélée aux données numismatiques et historiques. Des spécificités régionales ou locales du point de vue de la pureté des alliages monétaires ont été observées. L'examen des teneurs en éléments mineurs et traces caractéristiques, susceptibles de témoigner de mélanges ou de mouvements de stocks de métaux précieux, a mis en évidence des particularités de l'argent frappé par certains ateliers monétaires, en particulier celui de Venise.

La Spectrométrie de Masse à source Plasma à Couplage Inductif s'impose, de par ses multiples avantages, dont sa sensibilité et ses temps d'analyse réduits, comme la technique de spectrométrie de masse la plus répandue en analyse inorganique pour déterminer la concentration d'un isotope donné ou mesurer des rapports isotopiques. Le problème des interférences spectroscopiques, inhérent à cette technique, trouve une solution dans l'utilisation de dispositifs de collision-réaction. Une résolution in situ des interférences est en effet rendue possible par l'injection, dans la cellule de collision-réaction, d'un gaz judicieusement choisi. Les étapes de séparation chimiques, habituellement réalisées en amont de la mesure, et très pénalisantes dès lors que les échantillons manipulés sont radioactifs, peuvent ainsi être supprimées. La compréhension de la chimie des interactions « ions-molécules » en phase gazeuse est cependant primordiale pour optimiser l'efficacité de tels dispositifs. Pour cela, une connaissance précise des conditions expérimentales dans la zone de réaction s'avère cruciale, afin de pouvoir interpréter les réactivités observées.<br /><br />Deux ICP-MS de conception différente, l'ICP-MS Quadripolaire X7 (Thermo-Fisher Scientific) et l'ICP-MS Multi-Collection Isoprobe (GV Instruments), sont utilisés dans cette étude. Les conditions expérimentales, existant dans la cellule de collision-réaction de chacun de ces deux instruments, sont déterminées en fonction des paramètres instrumentaux. Cette étude préliminaire est ensuite mise à profit dans le cadre de la résolution de deux interférences, caractéristiques au domaine du nucléaire. Une approche théorique par calculs de chimie quantique permet d'interpréter la formation des oxydes de zirconium, responsable de la suppression de l'ion interférent 90Zr+, suite à l'utilisation d'O2 dans la cellule de collision-réaction pour permettre la mesure du radionucélide 90Sr. Le cas de la réactivité de cinq cations lanthanides (Nd, Sm, Eu, Gd, Dy) avec plusieurs gaz (O2, N2O, CO2, NH3) est par ailleurs étudié expérimentalement. L'efficacité de l'ammoniaque pour résoudre les interférences isobariques Eu/Gd est mise en évidence. Une périodicité de la réactivité sur la série des lanthanides, due à la configuration électronique de l'état fondamental des cations Ln+, est proposée pour expliquer les différences de comportements observées.

La composition élémentaire des coquilles de bivalves pourrait, selon la communauté scientifique internationale, être modulée par les variations spatiales ou temporelles du milieu ambiant tel la température, la salinité, la productivité primaire.... Toutefois, un ensemble de travaux ont mis en évidence que la présence des éléments mineurs et en traces dans les coquilles sont souvent spécifiques aux espèces considérées ou dépendent de plusieurs paramètres environnementaux. En conséquence, des recherches supplémentaires s'avèrent nécessaires afin de mieux comprendre la modalité d'incorporation de ces potentiels traceurs dans la matrice carbonatée. L'objectif de ce travail de thèse était de développer des méthodologies analytiques sur un spectromètre de masse haute-résolution couplée à une source plasma (HR-ICP-MS Element 2 de Finigan) pour déterminer quantitativement un nombre important d'éléments en traces dans des matrices de carbonate de calcium (CaCO3). Deux méthodes (le couplage LA-ICP-MS et l'analyse en mode liquide) ont été développées afin de placer sur une échelle calendaire (± 3 jours) les variations ontogéniques des teneurs élémentaires dans les valves de P. maximus. Les résultats d'analyses obtenus sur une même valve gauche par les deux méthodes, montrent que les profils élémentaires demeurent reproductibles quels que soient les concentrations rencontrées et le transect choisi sur la valve. Les teneurs élémentaires dans les valves de P. maximus mesurées sur l'ICP-MS Element 2 sont en accord avec les valeurs obtenues précédemment sur la même population et la même année de croissance lorsque l'on se réfère aux résultats pionniers acquis par le laboratoire de Pau (LA-ICP-MS quadripolaire) L'analyse en mode liquide de trois transects de croissance d'une même valve démontre que la distribution élémentaire est homogène dans la matrice carbonatée de la coquille Saint-Jacques. Les résultats d'analyses de deux éléments en traces (Mo et Li) dans les valves de P. maximus ont été détaillés. Les variations de la concentration valvaire en molybdène sont reproductibles entre plusieurs individus issus d'une même population pendant différentes années et lorsque différents écosystèmes côtiers bretons sont étudiés (Rade de Brest, baie de Saint-Brieuc et Belle-Ile en mer). Chaque profil varie à un niveau voisin des limites de détection de l'appareil de mesure, mais est ponctué par un voire deux enrichissements épisodiques printaniers (mai). Parmi toutes les hypothèses discutées pour expliquer ces événements (pics en Mo), l'ingestion de cellules phytoplanctoniques ayant utilisées les nitrates comme source d'azote apparait la plus vraisemblable (ces cellules présenteraient une concentration forte en Mo suite au rôle de Mo lors de l'activité enzymatique de la nitrate réductase) La faible variabilité inter-individuelle des concentrations valvaires en Li d'une même population suggère l'influence d'un paramètre environnemental ou physiologique pour expliquer l'incorporation du lithium au sein des valves. Toutefois, les variations ontogéniques de la teneur coquillière en lithium chez P. maximus diffèrent selon l'année étudiée. Certaines populations de P. maximus présentent de brusques augmentations transitoires de la teneur en Li pendant leur période de croissance. Notre étude n'a pas pu mettre en évidence un lien généralisable entre ces pics en Li et un paramètre environnemental. Cependant, ces enrichissements en Li semblent apparaître quelques jours après des floraisons phytoplanctoniques de diatomées. En outre, nous constatons que le bruit de fond de la teneur en Li serait majoritairement lié à la vitesse de croissance de l'animal.

Previous work by our research group demonstrated that quantitative chemical analysis of analytes, such as mercury and chromium species, in environmental matrices could be successfully carried out without using calibration curves and with correction for species interconversion by using EPA Method 6800A. This method encompasses isotope dilution mass spectrometry (IDMS) and speciated isotope dilution mass spectrometry (SIDMS), both of which are described in detail in chapter 1. Research described in this dissertation expands upon our earlier work by applying the method to the speciation of mercury in biological matrices, the speciation of glutathione in red blood cells and whole blood, and the analysis of enzyme activity in mammalian tissue. / Bayer School of Natural and Environmental Sciences; / Chemistry and Biochemistry; / PhD; / Dissertation;

Abstract Methods for tephrochronology are evaluated, in the following way: Lake sediments &lt;500 years old from three small Antarctic lakes were analysed for identification of tephras. Subsamples were analysed for a) grain size, and identification and concentration of volcanogenic grains, b) identification of tephra horizons, c) element abundance by EPMA WDS/EDS and LA-ICP-MS, and d) possible correlations between lakes and volcanoes. Volcanogenic minerals and shards were found all through the sediment cores in all three lakes, in different abundances. A high background population of volcanogenic mineral grains, in all samples, made the identification of tephra horizons difficult, and shards could only be distinguished by certainty after chemical analysis of elements. The tephra layers commonly could not be seen by the naked eye, and, hence they are regarded as cryptotephras. Because of the small size of recent eruptions in the research area, and the travel distance of ash, most shards are small and difficult to analyse. Nine possible tephra horizons have been recorded in the three lakes, and preliminary correlations have been made. But because of analytical problems, the proposed correlations between the lakes and possible volcanic sources are preliminary.