Made available in DSpace on 2014-10-09T12:54:14Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:09:24Z (GMT). No. of bitstreams: 1 12433.pdf: 20959730 bytes, checksum: a98e9829a642f5e597da179c95c176ef (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Quimica, Universidade de Sao Paulo - IQ/USP

Made available in DSpace on 2014-10-09T12:34:22Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:10:40Z (GMT). No. of bitstreams: 0 / O Brasil possui a sétima maior reserva geológica de urânio do mundo, com aproximadamente 310 mil toneladas. A Província Uranífera de Lagoa Real, na região de Caetité e Lagoa Real, situado no centro sul da Bahia, é considerada a mais importante província monominerálica do Brasil. A população urbana que vive no distrito uranífero nas cidades de Caetité, Lagoa Real e Livramento de Nossa Senhora usa água potável oriunda do abastecimento público. Na área rural, caracterizada por freqüentes secas, os moradores recebem água de poços escavados e perfurados como também, de pequenas barragens e reservatórios abastecidos pelas chuvas. Este trabalho determinou os níveis de radioatividade alfa e beta total e as concentrações de urânio em diversos tipos de água consumidas pela população urbana e rural da Província Uranífera de Lagoa Real. As atividades α e β total foram determinadas com detector proporcional de fluxo gasoso e baixa radiação de fundo. As concentrações de urânio foram determinadas com o Espectrômetro de Massa com Fonte de Plasma Indutivo (ICP-MS). Os resultados obtidos foram comparados com as recomendações recentes de 2011 da Organização Mundial da Saúde, a portaria nº 2914 de 12/12/2011 do Ministério da Saúde e as resoluções do CONAMA. Os níveis de radiação natural variaram de 0,0041 ± 0,0004 Bq.L-1 a 0,80 ± 0,04 Bq.L-1 para a atividade alfa total e de 0,045 ± 0,003 a 3,0 ± 0,2 Bq.L-1 para a atividade beta total. Tendo como parâmetro a OMS e o MS, apenas duas amostras de água subterrânea, uma localizada na cidade de Lagoa Real e outra na cidade de Caetité apresentaram concentrações alfa total acima do valor de 0,5 Bq.L-1 descrito em suas recomendações, 0,80 ± 0,04 Bq.L-1 e 0,57 ± 0,03 Bq.L-1respectivamente. Para beta total, três amostras apresentaram níveis de radioatividade acima do limite de 1 Bq.L-1 recomendado pela Organização Mundial de Saúde e estabelecido pelo Ministério da Saúde; 3,0 ± 0,2 Bq.L-1; 1,63 ± 0,13 Bq.L-1 e 1,19 ± 0,07 Bq.L-1 todos situados no município de Lagoa Real. Duas amostras de água subterrânea no município de Caetité apresentaram concentrações de urânio acima do valor de 15 μg.L-1 determinado pelo CONAMA, 20,3 ± 0,3 μg.L-1 e 17,1± 0,3 μg.L-1. Em Lagoa Real, uma amostra apresentou níveis de urânio seis vezes superior ao limite estabelecido pelo Conselho Nacional de Meio Ambiente, 89,5 ± 1,5 μg.L-1. A Organização Mundial da Saúde em 2004 estabeleceu em suas recomendações o limite de 15 μg.L-1 como a concentração máxima de urânio na água potável. Em 2011 a OMS aumentou este limite para 30 μg.L-1. Levando-se em consideração as atuais recomendações da OMS, apenas a concentração de uma amostra de água apresentou níveis de urânio acima do recomendado, 89,5 ± 1,5 μg.L-1 no município de Lagoa Real. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Submitted by Marcele Costal de Castro (costalcastro@gmail.com) on 2017-10-11T15:39:41Z No. of bitstreams: 1 ELIZABETH MASSENA FERREIRA D.PDF: 2256671 bytes, checksum: 0c292929bbb0f709ecda077644b77851 (MD5) / Made available in DSpace on 2017-10-11T15:39:41Z (GMT). No. of bitstreams: 1 ELIZABETH MASSENA FERREIRA D.PDF: 2256671 bytes, checksum: 0c292929bbb0f709ecda077644b77851 (MD5) Previous issue date: 2003-02 / Este trabalho apresenta um estudo sistemático da sorção de índio de meio iodeto, utilizando espuma de poliuretano à base de poliéter comercial como extrator em fase sólida, visando à pré-concentração e/ou separação de índio de diferentes matrizes de amostras. As características físico-químicas de sorção do sistema foram investigadas por processo em batelada, apresentando rápida cinética e máxima sorção numa faixa significativa de meio ácido ou básico, com coeficientes de distribuição acima de 104 L kg-1 ([KI] ≥ 0,6 mol L-1). A análise do equilíbrio de sorção indicou o tetraiodo-indato (MInI4) como a principal espécie sorvida na matriz da espuma; os mecanismos de sorção mais prováveis foram discutidos. A isoterma de Langmuir foi ajustada com êxito sendo obtido um valor de (1,55±0,02)x10-1 mol kg-1 para a capacidade de saturação. O efeito da temperatura foi avaliado indicando um processo espontâneo e exotérmico caracterizado por sorção química. A reextração do índio da espuma com solução de HCl 1,0 mol L-1 em meio etanol 50% apresentou rápida cinética (10 minutos) e eficiência (97%). O sistema pode ser utilizado para a separação de traços de índio de grandes quantidades de Al, Fe, Zn, Ni, Co, Mn e Ga. Cd e Pb são co-extraídos. Ácido cítrico, F- e EDTA interferem na sorção do índio; tiosulfato de sódio (< 0,1 mol L-1) e ácido ascórbico (até 0,8 mol L-1) não interferem. O sistema foi avaliado na determinação de In na presença de 105 vezes Zn, Al, Fe pelo método de adição e recuperação de índio. Os elementos determinados por ICP-OES apresentaram fatores de separação, da ordem de 7,0x 102 para Zn/In, 1,0x105 para Fe/In e de 5,5x104 para Al/In, com eficiente recuperação de índio. A metodologia desenvolvida foi aplicada para determinar índio por ICP-OES em material de referência padrão de zinco metálico (NIST), apresentando concordância compatível com o valor certificado, para um nível de confiança de 95%. / This work shows a systematic study on indium iodide sorption using commercial polyether-based polyurethane foam as a solid phase extractor in order to preconcentrate and/ or separate indium from different sample matrices. The physico-chemical characteristics of the system sorption were investigated for the batch process. The system has shown rapid kinetic and maximum sorption from a meaningful range of either acid or basic medium and achieves distribution ratios above 104 L kg-1 ([KI] ≥ 0.6 mol L-1). Sorption equilibrium analysis indicates the tetraiodo-indate (MInI4) as the main species sorbed on the foam matrix; the more probable mechanisms of sorption were discussed. Langmuir isotherm was successfully fitted and a value of (1.55±0.02)x10-1 mol kg-1 was obtained for the saturation capacity. The temperature effect was evaluated and indicates a spontaneous and exothermic chemisorption process favored at low temperatures. The indium reextraction from the foam using a HCl 0.1 mol L-1 in ethanol 50% medium solution has also shown a rapid kinetic (10 minutes) and efficiency (97%). The system should be used to separate large quantities of Al, Fe, Zn, Ni, Co, Mn and Ga from trace indium. Cd and Pb are coextracted with indium. Citric acid, F- and EDTA interfere on indium sorption; sodium thiosulfate (≤ 0.1 mol L-1) and ascorbic acid (up to 0.1 mol L-1) do not interfere. The system was evaluated in the determination of indium in the presence of 105 times Zn, Al and Fe by indium addition and recovery technique. The elements determination by ICP-OES showed separation factors around 7.0x102 for Zn/In, 1.0X105 for Fe/In and of 5.5x104 for Al/In, with an efficient recovery of indium. The developed methodology was applied to determine indium in metallic zinc standard reference material (NIST) by ICP-OES and has shown compatible agreement with the certified value at a 95% confidence level.

L'utilisation de lasers est largement répandue dans le domaine de la microanalyse directe des solides. La matière vaporisée, en focalisant un faisceau laser de forte puissance sur la cible, peut être analysée soit par spectrométrie d'émission optique sur plasma induit (LIBS, acronyme anglais pour Laser Induced Breakdown Spectroscopy), soit par une source à plasma induit par haute fréquence couplée à la spectrométrie d'émission optique (ICP-AES) ou à la spectrométrie de masse (ICP-MS). Avec une résolution spatiale à l'échelle microscopique, les techniques d'ablation laser permettent ainsi d'accéder à la composition élémentaire locale de la surface d'un matériau. Néanmoins, les performances analytiques de ces techniques pourraient être améliorées par l'utilisation combinée des informations LIBS et ICP afin également de comprendre et maîtriser davantage l'interaction laser/matière. Dans ce but, ce travail a consisté à développer une technique de microanalyse par ablation laser couplée avec une détection en simultané par ICP et par LIBS afin d'étudier les potentialités analytiques de cet instrument pour cartographier la surface des matériaux. Les performances et les limitations de ce système ont été évaluées d'une part, en caractérisant les aérosols produits par ablation laser et d'autre part, en étudiant les signaux LIBS et ICP obtenus à partir d'un même prélèvement de matière. Le phénomène de fractionnement élémentaire rencontré sur des matrices critiques telles que le laiton a été mis en évidence en microablation malgré des caractéristiques de l'interaction laser/matière différente de la macroablation. Une méthode de correction, a posteriori, par l'efficacité d'extraction de la cellule d'ablation a été proposée afin de pallier ces effets limitatifs pour l'analyse quantitative. Une cellule d'ablation, optimisée à partir d'une étude de simulation numérique, a été développée afin de s'adapter aux applications de cartographies de surface. Les performances analytiques du système ont été évaluées en termes de stabilité (8-10%), de résolution spatiale (5 µm) et de limites de détection (de l'ordre de la ppm dans le solide avec un détecteur de masse). La complémentarité des mesures LIBS et ICP représente à la fois un outil de diagnostic de l'interaction laser/matière et un instrument d’analyse très complet grâce à la double détection qui permet de suivre simultanément des traces et des majeurs sur une large gamme d'éléments de la classification périodique / Laser ablation is widely spread for solid sample microanalysis. A tightly focused laser beam allows direct sampling of matter, the ablated mass can then be analysed either with LIBS (Laser Induced Breakdown Spectroscopy) or with an inductively coupled plasma source combined with an optical emission spectrometer (ICP-AES) or a mass spectrometer (ICP-MS). With spatial resolution down to the micron scale, laser ablation techniques permit local elemental analysis of sample surface. Nevertheless, analytical performances of such techniques could be improved by combining LIBS and ICP information to understand and control laser/matter interaction. For this purpose, this work aimed to develop a microanalytical technique based on laser ablation coupled to simultaneous detection with LIBS and ICP to study analytical potentialities of such technique for elemental mapping of material surface. Performances and limitations of the system were studied on one hand, by characterizing laser-induced aerosols and on the other hand, by studying simultaneous LIBS and ICP signals. Elemental fractionation on critical matrices such as brass was evidenced in microablation despite a different laser/matter interaction compared with macroablation. A correction procedure a posteriori using the total extraction efficiency of the ablation cell was proposed to overcome this problem for quantitative analysis. An ablation cell, optimized from a numerical simulation study, was developed for mapping applications. Analytical performances were evaluated in terms of stability (8-10 %), spatial resolution (5 µm) and detection limits (in the ppm range with ICP-MS). The LIBS and ICP complementarity makes the double detection system a diagnostic tool for laser/matter interaction and an analytical instrument allowing simultaneous monitoring of traces and majors from a large element range of the periodic classification

An important step in the more efficient use of PICA (Phenolic Impregnated Carbon Ablator) as a Thermal Protection System (TPS) material for spacecraft is the understanding of its pyrolysis mechanics. The gases released during pyrolysis and their subsequent interaction with the reactive plasma environment is not yet well understood. The surface recession of PICA as it ablates during testing only makes the study and characterization of the chemical reactions more difficult. To this end, a probe has been designed for this study to simulate, in steady state, the pyrolysis gases within the UVM 30kW Inductively Coupled Plasma (ICP) Torch Facility. This probe, which is an extension of previous work done at UVM, has been used to inject Carbon Dioxide, Hydrogen, and a mixture of the two into pure Argon and dilute Nitrogen, Oxygen, and air plasmas. During testing, spatially resolved, pointwise, line of sight emission measurements were taken in the boundary layer region. These results were then compared to temporally resolved PICA emission data taken in a previous study. After the correct temporal PICA scan was found the data sets closely matched. This indicates that the gas-injection probe is a viable method to simulate pyrolysis in a steady state environment. The key pyrolysis species of CN, NH, OH, Hydrogen Alpha (Hα), and Hydrogen Beta (Hβ) were spatially traced along the stagnation line for the pure Hydrogen and mixture injection cases. These measurements show evidence of spatial relationships between NH and Hα as well as between OH and Hβ. They also show that all of the molecules tend to follow the same general trend spatially. The work done for this study has both reintegrated gas-injection capability into the UVM facility as well as laid the groundwork for future gas-injection testing within the facility. Spatial emission analysis techniques currently being developed at UVM will provide a more resolved picture of the interactions occurring in the boundary layer once completed.

The necessity of elemental analysis techniques to solve forensic problems continues to expand as the samples collected from crime scenes grow in complexity. Laser ablation ICP-MS (LA-ICP-MS) has been shown to provide a high degree of discrimination between samples that originate from different sources. In the first part of this research, two laser ablation ICP-MS systems were compared, one using a nanosecond laser and another a femtosecond laser source for the forensic analysis of glass. The results showed that femtosecond LA-ICP-MS did not provide significant improvements in terms of accuracy, precision and discrimination, however femtosecond LA-ICP-MS did provide lower detection limits. In addition, it was determined that even for femtosecond LA-ICP-MS an internal standard should be utilized to obtain accurate analytical results for glass analyses. In the second part, a method using laser induced breakdown spectroscopy (LIBS) for the forensic analysis of glass was shown to provide excellent discrimination for a glass set consisting of 41 automotive fragments. The discrimination power was compared to two of the leading elemental analysis techniques, µXRF and LA-ICP-MS, and the results were similar; all methods generated >99% discrimination and the pairs found indistinguishable were similar. An extensive data analysis approach for LIBS glass analyses was developed to minimize Type I and II errors en route to a recommendation of 10 ratios to be used for glass comparisons. Finally, a LA-ICP-MS method for the qualitative analysis and discrimination of gel ink sources was developed and tested for a set of ink samples. In the first discrimination study, qualitative analysis was used to obtain 95.6% discrimination for a blind study consisting of 45 black gel ink samples provided by the United States Secret Service. A 0.4% false exclusion (Type I) error rate and a 3.9% false inclusion (Type II) error rate was obtained for this discrimination study. In the second discrimination study, 99% discrimination power was achieved for a black gel ink pen set consisting of 24 self collected samples. The two pairs found to be indistinguishable came from the same source of origin (the same manufacturer and type of pen purchased in different locations). It was also found that gel ink from the same pen, regardless of the age, was indistinguishable as were gel ink pens (four pens) originating from the same pack.

As a consequence of the widespread use of computers coupled to high-quality printers and different types of papers, forgery, counterfeiting, change of wills, anonymous letter writing and felonious use of the documents have become serious problems. Forensic analysts are always seeking methods that can provide reliable information on whether a specimen collected at the crime scene is linked to the crime or to a source of known origin. Sensitive methods that can provide more detailed characterization of natural or man-made materials or even provide information not previously available to forensic examiners. Recent advances in rapid solid sampling of materials using laser ablation (LA) coupled to inductively coupled plasma mass spectroscopy (ICP-MS) have led to this analytical method to be regarded as the “gold standard” in the field of elemental analysis for trace level components in solids. Another, emerging, analytical technique that uses the same laser pulse to generate a plasma that can be interrogated with spectroscopy is laser induced break down spectroscopy (LIBS). The analysis of ink and paper is also possible because of the surface removal effect of laser interactions with the samples. In the present study, printing inks were analyzed using LIBS, LA-ICP-MS and both of them in tandem mode. In the tandem setup, the light generated during the relaxation of the excited species (LIBS) was used to create a spectral signature of the elements, and the mass-to-charge ratio of the ejected particles (ICP-MS) was used to create a mass spectrum. For a set of 319 printing ink samples, LA-ICP-MS alone provided discrimination greater than 99%. A subset of 43 printing inks, having a very similar elemental profile, was analyzed by tandem LIBS/LA-ICP-MS. The fusion of LIBS and LA-ICP-MS provided additional discrimination through the detection of elements like Ca, Si, Fe, and K by LIBS, that are difficult to detect and confirm using standalone ICP-MS because of the spectral interferences (isobaric and polyatomic) involved. The combination of these two sensors was found to minimize the individual limitations and provide a more complete and representative chemical characterization of printing inks.

Glass is a common form of trace evidence found at many scenes of crimes in the form of small fragments. These glass fragments can transfer to surrounding objects and/or persons and may provide forensic investigators valuable information to link a suspect to the scene of a crime. Since the elemental composition of different glass sources can be very similar, a highly discriminating technique is required to distinguish between fragments that have originated from different sources. The research presented here demonstrates that Laser Induced Breakdown Spectroscopy (LIBS) is a viable analytical technique for the association and discrimination of glass fragments. The first part of this research describes the optimization of the LIBS experiments including the use of different laser wavelengths to investigate laser-material interaction. The use of a 266 nm excitation laser provided the best analytical figures of merit with minimal damage to the sample. The resulting analytical figures of merit are presented. The second part of this research evaluated the sensitivity of LIBS to associate or discriminate float glass samples originating from the same manufacturing plants and produced at approximately the same time period. Two different sample sets were analyzed ranging in manufacturing dates from days to years apart. Eighteen (18) atomic emission lines corresponding to the elements Sr, K, Fe, Ca, Al, Ba, Na, Mg and Ti, were chosen because of their detection above the method detection limits and for presenting differences between the samples. Ten elemental ratios producing the most discrimination were selected for each set. When all the ratios are combined in a comparison, 99% of the possible pairs were discriminated using the optimized LIBS method generating typical analytical precisions of ~5% RSD. The final study consisted of the development of a new approach for the use of LIBS as a quantitative analysis of ultra-low volume solution analysis using aerosols and microdrops. Laser induced breakdown spectroscopy demonstrated to be an effective technique for the analysis of as low as 90 pL for microdrop LIBS with 1 pg absolute LOD and 20 µL for aerosol LIBS with an absolute LOD of ~100 fg.

Laboratory measurements of primitive and differentiated meteorites have been made in order to understand the origin of isotopic anomalies. The element Zr is chosen for analysis, due to its potential for nuclear and astrophysical applications. Zirconium has five stable isotopes that are produced in different (neutron–capture) nucleosynthetic processes. By analysing the Zr isotope composition of meteorites, we are able to track the mixing of various neutron capture processes in the early Solar System. Measurements have been performed on carbonaceous, ordinary and enstatite chondrites, eucrites, the Moon and Earth. Samples are crushed, digested and passed through a two stage anion exchange separation to obtain a clean Zr fraction. All Zr measurements are made on a Nu Plasma multiple–collector inductively coupled plasma mass spectrometer (MC–ICPMS). The results indicate that the bulk of refractory Ca–Al rich inclusions of the Allende meteorite are characterised by uniform enrichments (around 2ε) of the neutron–rich isotope 96Zr, and potentially coupled with excesses reported for the neutron rich isotope 50Ti, indicating that both nuclides may have similar astrophysical origins. Analysis of bulk rock carbonaceous chondrites reveal 96Zr excesses (not exceeding 1ε) that scale with the abundance of CAIs. However, widespread 96Zr correlations are also seen, accompanied by minor depletions in 91Zr, which suggest the solar nebular had experienced thermal heating of some sort, altering the initial (possibly uniform) Zr isotope composition of the early Solar System from which planetary bodies formed.

Iron is ubiquitous in the environment, ranking fourth in abundance in the earth's crust. Iron is responsible for many environmental mechanisms including the distribution of plant nutrients and pollutants. Iron can exist in several minerals, including iron oxides. Arsenic is a naturally occurring metalloid which has been confirmed by the EPA as a carcinogen. Recently, an arsenic epidemic has unfurled in Bangladesh, poisoning an estimated 70 million people. Arsenic contamination does not exist only in the third world, but also in the United States, including Iowa. Due to the widespread distribution of arsenic and the potential for it to be leached into groundwater supplies, there has been a growing interest in establishing removal mechanisms. Atomic absorption (AA) spectroscopy and inductively coupled plasma optical emission spectrometry (ICP-OES) have been used. There has been a shift in arsenic analysis methods with the advent of more sensitive methods such as the inductively coupled plasma mass spectrometer (ICP-MS). The geology department recently acquired a Thermo Scientific XSERIES ICP-MS, so an arsenic analysis method was developed in preparation for the research conducted in this study. The ICP-MS, however, only measures total arsenic concentration. As this study focused on the oxidation state of arsenic, an alternative means for determining oxidation state was developed. As(V)-selective cartridges were used to adsorb arsenate, while letting arsenite run through. This method was checked for effectiveness and used to determine aqueous arsenic oxidation state. X-ray absorption spectroscopy (XAS) was used to determine the oxidation state of arsenic adsorbed onto the surface of iron oxide. Goethite (α-FeOOH) and magnetite (Fe3O4) are both known to strongly adsorb arsenic. In this work, the potential for As(III) oxidation and As(V) reduction by goethite was studied. As documented by Amstaetter et al., there was some evidence for adsorbed As(III) oxidation by an Fe(II)/goethite system. This study, however, also showed some evidence for oxidation of adsorbed arsenite in the presence of goethite alone. As(V) reduction by magnetite was also studied. Magnetite is capable of having different stoichiometries, or ratios of Fe(II) to Fe(III). Both an oxidized, x=0.27, and a near-stoichiometric, x=0.49, magnetite were studied for their ability to reduce arsenate. There was no evidence for As(V) reduction in the aqueous or adsorbed phase for either system.