Ultrasonic slurry sampling electrothermal vaporization dynamic reaction cellTM inductively coupled plasma mass spectrometry (USS-ETV-DRC-ICP-MS) has been applied to the determination of As and Se in soil and sediment samples. The influences of instrument operating conditions and slurry preparation on the ion signals were reported. Ascorbic acid and Pd were used as the modifiers to enhance the ion signals. The background ions at the selenium masses were reduced in intensity significantly by using 1.5 ml min-1 H2 as reaction cell gas in the DRC while a q value of 0.65 was used. Since the sensitivities of As and Se in slurry solution and aqueous solution were quite different, standard addition method was used for the determination of As and Se in these samples. This method has been applied to the determination of As and Se in NIST SRM 2711 Montana soil and SRM 2709 San Joaquin soil reference materials and NRCC BCSS-1 marine sediment reference sample. The analysis results of the reference materials were agreed with the certified values. The method detection limits estimated from standard addition curves were about 0.046-0.082 and 0.019-0.024 mg g-1 for As and Se, respectively, in original soil and sediment samples.

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La première partie de cette étude concerne la distribution de Nb et Ta à l'échelle microscopique dans les roches mantelliques. On a mesuré à la microsonde électronique leurs concentrations dans des microphases titanifères (rutile), afin d'étudier le rôle de ces phases dans le fractionnement des deux éléments.<br />La seconde partie concerne la distribution de Nb et Ta dans les différentes enveloppes terrestres. A partir d'analyses en roche totale par ICP-MS, on a étudié les variations des rapports Nb/Ta, Nb/Th et Ta/La dans les grands réservoirs géochimiques représentant la Terre Silicatée. La plupart ont un rapport Nb/Ta moyen infrachondritique (< 17,5). Seule la couche lithosphérique située à l'interface croûte-manteau se distingue par des rapports Nb/Ta suprachondritiques, attribués à la migration de faibles fractions de liquides enrichis en volatiles. Cependant, cette couche, peu épaisse et faiblement concentrée en Nb et Ta, ne peut contrebalancer les valeurs infrachondritiques des autres réservoirs.<br />Trois raisons nous conduisent à réfuter l'hypothèse d'un réservoir à Nb/Ta élevé « caché » dans le manteau convectif et alimenté par les zones de subduction, proposée pour contrebalancer ces valeurs infrachondritiques: (1) la valeur moyenne de Nb/Ta dans les arcs n'est pas significativement inférieure à celle des basaltes océaniques, (2) les valeurs faibles de Nb/Ta dans la croûte continentale ne sont pas un héritage de la subduction mais l'aboutissement de la différenciation intracrustale et (3) l'étude des basaltes océaniques n'a pas révélé de composant mantellique à Nb/Ta élevé dans leur source.<br />Finalement, l'inversion des données de Nb, Ta, Th et La à l'échelle de la planète montre qu'une incorporation de Nb dans le noyau peut expliquer le rapport infrachondritique de la Terre Silicatée. Les résultats fournissent une estimation du coefficient de partage de Nb entre noyau et manteau primitif de 0,25 ± 0.08, en accord avec les données expérimentales récentes.

Plazas and patios were important spaces for expressing power and social identity in prehispanic Mesoamerica. However, plazas can be analytically problematic, because they were often kept clean of material debris. Previous geoarchaeological studies of anthropogenic soils and sediments have shown that specific activities leave characteristic chemical signatures on prepared earthen surfaces. The research presented here uses soil chemical residue analysis and excavation data to examine use patterns in the North Plaza of Palmarejo, Honduras during the Late Classic period. The goal is to determine whether the plaza was used for residential or ceremonial purposes. The chemical results indicate that activities in the northern half of the plaza were distinct from those that occurred in the southern half. These results, along with the artifact assemblage recovered from excavations, suggest ceremonial use. Additionally, this research compares various soil properties, including pH and organic matter, from the North Plaza to broaden our reach in prospecting for activity loci using soil chemistry. Recent studies tend to rely on spatial differences in elemental concentrations for identifying activity patterns in the archaeological record. However, other related soil properties sometimes correlate with chemical residues, especially phosphates. The research presented explores these interconnections with the greater goal of identifying the ways and extent to which various soil properties are linked in the formation and preservation of ancient activity loci. Results suggest that the deposition and adsorption of chemical residues in anthropogenic soils at Palmarejo are generally too variable to be accurately characterized by either pH or organic matter. Chemical elements may best reveal the use of the North Plaza in antiquity.

Sarahsaurus aurifontanalis is the most recent sauropodomorph dinosaur to be discovered and named from the Early Jurassic of North America. The dinosaur is represented by a mostly complete and articulated holotype specimen that preserves a unique manual phalangeal count of 2-3-4-2-2 and accessory pubic foramen adjacent to the obturator foramen. The holotype of Sarahsaurus comprises a braincase and isolated cranial elements, but the skull previously referred to this taxon, MCZ 8893, can only be provisionally referred to Sarahsaurus until additional crania are found associated with postcranial material. Sarahsaurus comes from the middle third of the Kayenta Formation, which is considered to be Early Jurassic in age despite the absence of a radiometric date from that unit. A new technique used to obtain a U-Pb radiometric date from the type quarry of Sarahsaurus in the Kayenta Formation was influenced by secondary uranium enrichment in the open system of the fossil bone. That suggests that uranium within the Kayenta Formation may be the result of the movement of groundwater during the Laramide orogeny in the Late Cretaceous and Early Eocene, and lends support to the hypothesis that the uplift of the Colorado Plateau began relatively early in Late Cretaceous to the Eocene. / text

The sorption behavior of yttrium and the rare earth elements (YREEs) was investigated using a variety of hydroxide precipitates over a range of solution conditions. Experiments with amorphous hydroxides of Al, Ga, and In were conducted at constant pH (~6.0) and constant ionic strength (I = 0.01 M), while YREE sorption by amorphous ferric hydroxide was examined over a range of ionic strength (0.01 M <̲ I <̲ 0.09 M), pH (3.9 <̲ pH <̲ 7.1), carbonate concentration (0 M <̲ [CO32-]T <̲ 150 micro-M), and temperature (10°C <̲ T <̲ 40°C). Sorption results were quantified via distribution coefficients, expressed as ratios of YREE concentrations between the solid and the solution, and normalized to concentrations of the sorptive solid substrate. Distribution coefficient patterns for Al, Ga, and In hydroxides were well correlated with the pattern for YREE hydrolysis. In contrast, amorphous ferric hydroxide developed a distinct pattern that was different than those for Al, Ga, and In precipitates but similar to the pattern predicted for natural marine particles. YREE sorption was shown to be strongly dependent on pH and carbonate concentration, significantly dependent on temperature, and weakly dependent on ionic strength. Distribution coefficients for amorphous ferric hydroxide (iKFe) were used to develop a surface complexation model that contained (i) two equilibrium constants for sorption of free YREE ions (M3+) by surface hydroxyl groups, (ii) one equilibrium constant for sorption of YREE carbonate complexes (MCO3+), (iii) solution complexation constants for YREE carbonates and bicarbonates, (iv) a surface protonation constant for amorphous ferric hydroxide, and (v) enthalpies for M3+ sorption. This quantitative model accurately described (i) an increase in iKFe with increasing pH, (ii) an initial increase in iKFe with increasing carbonate concentration due to sorption of MCO3+, in addition to M3+, (iii) a subsequent decrease in iKFe due to increasing YREE complexation by carbonate ions (especially extensive for the heavy REEs), and (iv) an increase in iKFe with increasing temperature.

The MP-AES 4200 using microwave plasma and an atomic emission spectroscopy detector provide a new and improved instrument to the analytical field. In this project will the performance of the equipment be evaluated in controlled NaCl-heavy matrices for selected metals (Cu, Zn, Li) and the result from this will be used to optimize a method for specific samples. These samples consist of combustion ashes from the incineration of hazardous waste and are provided by the company SAKAB AB. The sample preparation consisted of several cycles of L/S 10 followed by microwave assisted dissolution with concentrated HNO3, aqua regia or 18.2 MΩ. An extended amount of metals were quantified for these samples (Al, As, Ba, Ca, Cd, Cr, Cu, Fe, K, Li, Mn, Na, Ni, Pb, V, Zn) and most (not Ca, Li, K or Na) were compared with an ICP-MS instrument equipped with a collision cell used for the elements As, Fe and V. A final experiment was made on an L/S 10 of the samples to attempt to separate the metals from the salt with ion exchange, something that would make it possible to recycle this otherwise unused waste. The detection limits were all in the low μg L-1 except for Cd, Mn and Zn, which were between 2-4 μg L-1. The MP-AES was found to be able to handle matrices up to 5 g L-1 NaCl without a significant loss of response and provided near identical results to the ICP-MS for the elements that could be compared, this did not included the elements not quantified with the ICP-MS or V which was the only element under the limit of detection for the MP-AES. The experiment where an attempt was made to separate the metals from the salt was proven successful after treatment of bark compost and another type of waste ash as cation exchangers.

This study provides an insight into a provincial region of a developing country, namely Río Negro, Argentina and possible links between diet, environmental factors (especially water quality) and human health. Measuring levels of trace elements in scalp hair is a known method for assessing nutritional status. Levels of Ca, Fe, Mg, K, Na, As, Cr, Co, Cu, I, Mn, Mo, Ni, Se, V, Zn, Al, Cd, Pb, Rb and Hg in scalp hair from adolescents of the age 14 to 18 years in a rural and an urban population of Río Negro were analysed by inductively coupled plasma mass spectroscopy (ICP-MS). The hypothesis is that levels of trace elements reflect lifestyle factors such as smoking, beverage and food selection and consumption patterns and are directly linked to dehydration and could be associated with future health problems. Furthermore, environmental factors, such as (i) indecent water systems and governmental subsidised food in the rural/urban population, and (ii) ingestion or inhalation of arsenic (from naturally high sources of water, dust and foodstuffs) may also be linked to present and future health problems. The relationship between environmental and dietary factors could be implicated with the onset of diseases such as diabetes type II, obesity or hypothyroidism. The results show that both study populations in the region are exposed to several trace elements in exceedingly high amounts such as As and Mn through tap water which may induce cancers. Also, regular soft drink consumption is associated with low Cr level in this population. Evidence was not obtained for assessing potential dehydration. In terms of understanding the relationship between these factors, methods for assessing dehydration and dietary consumption need to be perfected, and other demographic issues and methods for quantifying obesity and health status will require further research.

This thesis describes the synthesis and characterization of metal-encoded polystyrene microspheres with a narrow size distribution designed for mass cytometry-based immuno- and oligonucleotide-assays. These particles were prepared by multiple stage dispersion polymerization techniques using polyvinylpyrrolidone (PVP) as a steric stabilizer. As a cytometeric technique, mass cytometry necessitated metal-encoded microspheres to perform the same roles of fluorescent microspheres used in conventional flow cytometry. The first role of the microsphere was to be able to act as a platform (classifier microspheres) for bioassays. Secondly, the microspheres should be suitable for mass cytometry machine calibration as standards. To perform these roles, metal-encoded microspheres were required to have certain size, functionality and metal content criteria. Lanthanide elements were chosen as the metals for encoding the microspheres for their low natural abundance in biological systems and for their similar chemistry. My goal was to employ two-stage dispersion polymerization, of styrene in ethanol, to introduce the lanthanide salts along with excess acrylic acid in the second stage, one hour after the initiation. Acrylic acid deemed to serve as a ligand for the lanthanide ions, through its carbonyl group, so the lanthanide ions get incorporated into the microsphere while acrylic acid is copolymerizing with styrene. Using two-stage dispersion polymerization, I could synthesize lanthanide encoded microspheres with narrow size distribution and high lanthanide content. However the lanthanide content distributions were unexpectedly much broader than the size distribution obtained. In addition, I could not attach biomolecules to the surface of such particles. In an attempt to improve the characteristics of these microspheres, I employed modified versions of multiple stage dispersion polymerization and seeded emulsion polymerization to grow functional polymer shell on the surface of the particles prepared by dispersion polymerization. Moreover, I coated the lanthanide encoded microspheres with silica shell which enabled me to grow another layer of functional-silica. Consequently, I could use these particles as classifier microspheres for mass cytometry-based immunoassays as well as fluorescence-based oligonucleotide-assays.

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