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Made available in DSpace on 2014-10-09T12:51:45Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:59Z (GMT). No. of bitstreams: 0 / O Brasil tem uma longa tradição na tecnologia do tório, desde a abertura do principal mineral, a monazita, até compostos de pureza grau nuclear, com reservas minerais estimados em 1.200.000 ton – ThO2. Como conseqüência desta produção, foi acumulado um resíduo produzido na unidade piloto de purificação de nitrato de tório, do Instituto de Pesquisas Energéticas e Nucleares- CNEN/SP, mais de 25 toneladas ao longo das últimas três décadas, proveniente dos rafinados e soluções de lavagem do processo de extração por solventes, conhecido como RETOTER. Sua composição, um hidróxido, contendo tório, terras raras e impurezas menores, incluindo o chumbo-208 do decaimento do 232 Th, com abundância isotópica em 88,34 %, enriquecido naturalmente ao longo das eras geológicas. Neste trabalho são discutidos os estudos dos principais parâmetros do processo de recuperação deste chumbo, 0,42 % em massa no RETOTER seco, utilizando-se a técnica de troca iônica com resinas aniônicas em meio clorídrico. A abundância isotópica do chumbo foi analisada por espectrometria de massa termoiônica (TIMS) e de alta resolução (ICPMS), e com os dados calculou-se a secção de choque de captura para nêutrons térmicos. O valor resultante foi de s? o = 14,6 +/- 0,7 mb diferentemente do chumbo natural de s? o = 174,2 +/- 7,0 mb. Estudos preliminares de recuperação do tório e terras raras neste resíduo também foram apresentados. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

L’acquisition de données structurales et thermodynamiques relatives à des systèmes actinides (An(III), Pu(IV) Pa(V))–acides organiques polyfonctionnels (citrique, NTA, DTPA), en solution aqueuse, vise à une meilleure compréhension des interactions actinides-ligands essentielle à l’optimisation de procédés de séparation, de décorporation, et également à l’évaluation de la sûreté des sites de stockage de déchets radioactifs. Le comportement du protactinium pentavalent à l’échelle des traces en présence des anions citrates et NTA a fait l’objet d’études systématiques par extraction liquide-liquide dans le système TTA/Toluène/HClO₄/NaClO₄/Pa(V)/ligands. Après avoir déterminé l’ordre limite des complexes (3 pour Pa(V)-Cit et 2 pour Pa(V)-NTA), les constantes de formation associées à chaque espèce ont pu être calculées. L’étude multi-technique (électrophorèse capillaire et spectrofluométrie laser) sur la complexation des An(III) par le DTPA, réalisée à plusieurs pH, a permis de mettre en évidence la coexistence des complexes mono-protoné (AnHDTPA–) et déprotoné. (AnDTPA²–) pour des solutions acides et faiblement acides. Une réinterprétation des données de la littérature, en considérant les deux complexes, a permis de faire converger les valeurs des constantes de complexation des espèces qui étaient jusqu’à maintenant dispersées. L’étude thermodynamique a ensuite été complétée par une étude théorique (calculs DFT). La structure des complexes protoné et non protoné et le mode de coordination du Curium ont ainsi été établis. L’étude exploratoire sur la complexation du Pu(IV) par le DTPA dans des conditions de pH proches du milieu biologique a nécessité le développement d’un protocole expérimental en trois étapes : protection de Pu(IV) contre l’hydrolyse avec NTA (pH faible), augmentation du pH vers des conditions neutres, compétition entre la complexation de Pu(IV) par le NTA et le DTPA. Les expériences préliminaires réalisées entre pH 1,5 et 3,5 par électrophorèse capillaire (EC-ICP-MS), semblent indiquer l’existence d’effet cinétique ou/et l’existence d’un complexe mixte. Les interprétations faites lors de cette étude exploratoire sont à confirmer. / A thorough knowledge of the chemical properties of actinides is now required in a wide variety of fields: extraction processes involved in spent fuel reprocessing, groundwater in the vicinity of radioactive waste packages, environmental and biological media in the case of accidental release of radionuclides. In this context, the present work has been focused on the complexation of Am(III), Cm(III), Cf(III), Pu(IV) and Pa(V) with organic ligands: DTPA, NTA and citric acid. The complexation of pentavalent protactinium with citric and nitrilotriacetic acids was studied using liquid-liquid extraction with the element at tracer scale (CPa < 10-10M). The order and the mean charge of each complex were determined from the analysis of the systematic variations of the distribution coefficient of Pa(V) as function of ligand and proton concentration. Then, the apparent formation constants related of the so-identified complexes were calculated. The complexation of trivalent actinides with DTPA was studied by fluorescence spectroscopy (TRLFS) and capillary electrophoresis (CE-ICP-MS). The coexistence of the mono-protonated and non-protonated complexes (AnHDTPA– and AnDTPA²–) in acidic media (1.5 ≤ pH ≤ 3.5) was shown unambiguously. Literature data have been reinterpreted by taking into account both complexes and a consistent set of formation constants of An(III)-DTPA has been obtained. The experimental study was completed by theoretical calculations (DFT) on Cm-DTPA system. The coordination geometry of Cm in CmDTPA²- and CmHDTPA- including water molecules in the first coordination sphere has been determined as well as interatomic distances. Finally, a study on the complexation of Pu(IV) with DTPA was initiated in order to more closely mimic physiological conditions. A three-step approach was proposed to avoid plutonium hydrolysis: i/ complexation of Pu(IV) with (NTA) in order to protect Pu(IV) from hydrolysis (at low pH) ii/ increase of pH toward neutral conditions and iii/ competition between the complexation of Pu with NTA and with DTPA. The preliminary experiments performed with CE-ICP-MS in the pH range 1.5 - 3.5 tend to indicate kinetic effect or/and the presence of mixed complex.

This diploma thesis deals with actual issues of the contamination in the environment with synthetic fragrances. Musk compounds are infiltrated to many environmental components (especially an aquatic ecosystem) because of their biological persistence and the ability of accumulation. This diploma thesis is focused on the selection and the optimization of method for the determination of musk compounds in real biotic matrices (fish). The isolation of analytes was realized by PSE method and the purification of extract was realized by the method of the adsorption column chromatography. Identification and quantification of individual musk compounds was carried out by GC-MS. In conclusion were results and the contamination of fish from the river Svratka disscissed and evaluated. These fish were caught at the inflow and at the outflow of the wastewater treatment plant.

This work was focused on the determination of musk compounds in various components of the environment. Synthetic musk compounds are organic substances commonly used as fragrant constituents of detergents, perfumes, cosmetics and other personal care products (PCPs). These compounds contaminate the aquatic environment through municipal wastewater from sewage treatment plants. The result is accumulation of these analytes in the environment and their occurrence in food chain. Synthetic fragrances are commonly detected also in human body; these substances generally belong among relatively new persistent organic pollutants (POPs) because of their persistence, bioaccumulation, and potential toxicity. The aim of this work was to optimize the methods for the determination of selected synthetic fragrances in wastewater (municipal, industrial) and in fish muscle. These analytes were determined in wastewater [the wastewater treatment plant (WWTP) Brno – Modřice, cosmetic manufacturing plant] and in fish Squalius cephalus that had been caught in the river Svratka. The selected analytes (14 substances) originate from the group of nitromusk, polycyclic musk and linear musk compounds. Solid phase microextraction (SPME) [for wastewater samples] and pressurized solvent extraction (PSE) [for fish samples] were used for isolation of analytes from real samples. The identification and quantification of analytes were carried out by high resolution gas chromatography coupled with mass spectrometry detection (GC-MS). The results show that galaxolide (g.L-1) and tonalide (tenths of g.L-1) were polycyclic musk compounds which were found at the highest concentration level in influent and also in effluent samples from the WWTP Brno – Modřice. The most extended nitromusk compound was musk ketone (hundredths of g.L-1). Linear musk compounds were detected in all influent samples (g.L-1). The overall removal efficiency of synthetic musk compounds from wastewater in the WWTP varies within the following ranges: nitromusk compounds 34.4 % – 85.4 %, polycyclic musk compounds 36.7 % – 53.3 % and linear musk compounds 90.5 % – 99.9 %. On the basis of the results it can be stated that wastewater (effluent from the WWTP) is the primary source of musk compounds, especially of the polycyclic ones in the environment. It has been also shown that ultrafiltration used in a cosmetic plant is a highly efficient technology for removing nitromusk and polycyclic musk compounds from industry wastewater. The results from evaluation of the fish contamination by musk compounds show that galaxolide was the substance which reached the highest concentration levels (tens of g.kg-1 l.w.). The results corroborate ubiquitous occurrence of musk compounds in the environment and reduction of using of nitromusk compounds due to their potential toxic properties. It has been shown that the insufficiency of the purifying procedures used in the WWTP Brno – Modřice has a significant influence on the concentration level of polycyclic musk compounds (tonalide, galaxolide) in fish caught from the river Svratka.

This thesis pertains to two R&D objectives associated with deploying TMFD sensor technology for meeting AARST-NRPP metrics for Radon (Rn) in-air detection, as well as for monitoring of ultra-trace actinides in air, amidst other Rn-progeny alpha emitting radionuclides. A challenge has persisted over the past 40+ years for detecting trace actinides in air amidst a 100-1000x higher Rn-progeny background. This thesis had a primary aim for addressing this challenge, and developing and assessing for a novel technology solution. Both objectives were successfully met. Methods, designs, and experimental effects of apparatus are discussed for successful Rn and progeny detection for 1-100 pCi/L concentration levels, as well as for Rn-progeny “blind” spectroscopic detection of 10-12 μCi/cc concentrations of actinides (Pu/U/Am) in air. The resulting CTMFD based technology was compared with the state-of-art “Alpha Sentry” CAM system and found to offer superior performance in multiple categories, and ~18x improvement in time to detect (e.g. at 0.02 DAC in 3 hrs vs ~70 hrs for state-of-art) for actinides while also remaining ~100% blind to ~102x higher Rn-progeny background; and, with 1 keV energy resolution vs ~300-400 keV for Alpha Sentry.

No description available.

Soil that is heavily contaminated with polycyclic aromatic hydrocarbons (PAHs) is often found at the sites of former gasworks and wood-impregnation plants. Since PAHs are toxic these sites represent a hazard to human health and the environment, and therefore they need to be treated, preferably by a method that destroys the contaminants, and thus eliminates the problem permanently. However, during biological and chemical degradation of PAHs other toxic compounds may be formed. If these transformation products are sufficiently persistent they could potentially accumulate during remedial processes. In the work underlying this thesis the degradation and transformation of PAHs were studied in three remedial processes: viz. a pilot-scale bioslurry reactor, microcosms with wood-rotting fungi and lab-scale treatments with Fenton's reagent. A group of transformation products referred to as oxygenated-PAHs (oxy-PAHs) was found to be particularly important, as these compounds are toxic and were shown to be relatively persistent in the environment. The oxy- PAHs were, for instance, found at significant concentrations in the gasworks soil used in most of the studies. This soil was highly weathered and had therefore been depleted of the more readily degradable compounds. In addition, experiments in which earthworms were exposed to the gasworks soil showed that the oxy-PAHs were more easily taken up in living organisms than PAHs. To facilitate the studies, new extraction and fractionation methods were developed. For instance, pressurized liquid extraction (PLE) was investigated for its reliability and efficiency to extract PAHs and oxy-PAHs from soil. Furthermore, a selective PLE-method was developed that can simultaneously extract and separate the PAHs and oxy-PAHs into two different fractions. This was accomplished by adding a chromatographic material (silica or Florisil) to the extraction cell. Under certain conditions all three remedial processes resulted in increasing amounts of oxy- PAHs in the soil. For example, 1-acenaphthenone and 4-oxapyrene-5-one accumulated in the bioslurry reactor. Similarly, in the soil inoculated with a white-rot fungus 9-fluorenone, benzo[a]anthracene-7,12-dione, 4-hydroxy-9-fluorenone and 4-oxapyrene-5-one accumulated. Finally, in an ethanol-Fenton treatment the concentration of some PAH-quinones increased in the soil. The results show that it might be necessary to monitor oxy-PAHs as well as PAHs during the remediation of PAH-contaminated sites. Otherwise, the soil may be considered detoxified too early in the process. In the long term it would be desirable to include analyses with sufficient marker compounds to follow the possible production and elimination of the oxy-PAHs. However, until such compounds can be identified it is suggested that contaminated soil should be screened for oxy-PAHs in general. The selective PLE-method presented in this thesis could be a useful tool for this.

The preparation of polymeric hybrid composite consisting of organic and inorganic fillers is of interest for industries like automotive, construction and packaging. In order to understand and predict the physical and chemical properties of these hybrid composites, it is necessary to fully understand the nature and properties of the employed fillers. In this study, the preparation of polypropylene hybrid composite consisting of wheat straw and clay was investigated. A detailed study was performed on wheat straw from South Western Ontario region. The effect of grinding the straw and compounding it with polypropylene was investigated. Experiments were carried out to identify the thermal stability of the ground wheat straw with respect to their size and composition. It was important to identify a correlation between these properties in order to minimize the straw degradation by processing and also to improve the final properties of the hybrid composite. The composite samples were prepared through melt blending method using a co-rotating twin-screw extruder. Sample test bars were prepared by injection moulding. The composition of the constituents of the hybrid composite; percentages of wheat straw, clay and coupling agent, were varied in order to investigate their influence on thermal stability, water resistance and mechanical properties. The results of the study indicated that grinding the wheat straw with a hammer mill produced particles with different sizes and shapes. It was found that through the grinding system all particles, regardless of their size, had a multi-layered structure similar to the plant structure. Further hammer milling did not produce plant particles with long aspect ratios that would be expected in a defibrillation process. Analysis of the chemical composition of wheat straw particles of different sizes and shapes was used to measure the ratio of hemicelluloses: lignin and the ash content. It was found that the large particles contained more amount of lignin whereas smaller particles had larger amount of ash content. The thermal stability of the particles was found to be a function of particle size rather than the lignin content. Particle size analysis on the wheat straw particles after the extrusion process indicated a reduction in the particle length and aspect ratio. The thermal stability of the composites was found to be enhanced by the addition of clay particles at higher temperature and the addition of coupling agent at lower temperatures. Increasing the amount of wheat straw and clay content increased the flexural modulus and reduced the resistance for water absorption. Increasing the amount of coupling agent also increased the flexural modulus and resistance for water absorption. The morphological study by scanning electron microscopy revealed that coupling agent increased the interfacial interaction between the particles and the polymer matrix.