Thesis (Ph. D.)--University of Missouri-Columbia, 2002. / Typescript. Vita. Includes bibliographical references (leaves 122-128). Also available on the Internet.

Thesis (M.S.)--Miami University, Dept. of Physics, 2008. / Title from first page of PDF document. Includes bibliographical references (p. 36-37).

Après un accident nucléaire tel que Fukushima en 2011, le césium 137 radioactif est transporté de l’atmosphère vers le sol par l’eau de pluie. Les argiles sont des espèces minérales finement divisées (1-100 µm) naturellement présentes dans les sols qui sont connues pour leurs propriétés adsorbantes sélectives et irréversibles vis-à-vis des ions Cs. L’objectif de la thèse est d’explorer la faisabilité d’un procédé, appelé flottation, pour l’extraction sélective des fines particules d’argile contaminée afin de réduire le volume de terres à stocker. La flottation consiste à séparer les espèces en fonction de leurs propriétés de surface. Les particules les plus hydrophobes sont collectées par les bulles d’air et transportées dans la mousse tandis que les particules hydrophiles restent en suspension. Des tensioactifs cationiques sont employés pour s’adsorber de façon sélective à la surface des argiles et augmenter leur degré d’hydrophobie. L’argile illite et le tensioactif TTAB de type bromure d’ammonium ont été sélectionnés pour l’étude. Les propriétés des suspensions d’illite/TTAB ont été déterminées (granulométrie, potentiel zêta…). Les mousses ont ensuite été étudiées à l’échelle laboratoire. Nous avons montré que les particules d’argile avaient bien un effet stabilisant sur la mousse. Par ailleurs, une sélectivité pour les fines particules (3 µm) est observée dans les mousses. La 2nde partie du travail a consisté à contribuer au développement d’une colonne de flottation fonctionnant en continu et à réaliser des essais sur le système illite/TTAB. L’influence des paramètres de concentration et de granulométrie de l’argile, de concentration en TTAB et de débit d’air sur les rendements d’extraction et les propriétés drainantes de la mousse a été étudiée. Grâce à cette étude, deux paramètres de transport ont été dissociés et extraits : la constante de flottation vraie et le coefficient de drainage qui sont ensuite employés pour une étude de dimensionnement de colonne de flottation industrielle. / After a nuclear accident like Fukushima, the radioactive cesium 137 is transported from the atmosphere to the soil by rain water. Clays are mineral species which are naturally present in soils. These micrometric minerals (1- 100 µm) are very efficient and selective adsorbents for Cs ions. The objective of this PhD thesis is to look at the feasibility of a process called flotation to selectively extract these contaminated clay particles and to reduce the volume of soil to store. Flotation consists in separating minerals according to their surface properties. The most hydrophobic particles are collected by air bubbles and are transported up to the froth whereas the hydrophilic particles remain in the suspension. Cationic surfactants are employed to selectively adsorb on clays surface and increase its hydrophobicity. It was chosen to focus on systems containing illite clay and an ammonium bromide cationic surfactant called TTAB. The properties of illite and TTAB suspensions were determined (particle size, zeta potential, adsorption isotherm of TTAB, turbidity, rheology). Then, foaming ability, stability and drainage properties of these suspensions were looked at by using a lab scale instrumented column. It was shown that clay particles have a stabilizing effect on the froth. Moreover, selectivity for the smallest clay particle size fraction (3 µm) in foams was observed. The 2nd part of the work consisted in performing flotation experiments on illite clay and TTAB suspension with a new “mini” pilot flotation column in continuous mode. The influence of TTAB concentration, air flow and illite clay concentration and granulometry on foam drainage properties and extraction yields was determined. From this study, two transport parameters were dissociated and extracted: the true flotation rate constant and the drainage coefficient. Finally, they were used to perform a scale-up study of an industrial flotation unit.

No description available.

Ce travail concerne la synthèse, les études des propriétés photophysiques et de complexation des molécules fluorescentes pour la détection sélective de cations toxiques tels que le césium, l'uranyle et l'arsenic. Tout d'abord, deux nouveaux capteurs fluorescents pour le césium, Calix-COU-P et Calix-COU-Benz-CN, comportant le Calix[4]arène-couronne-6 et le fluorophore coumarine ont été synthétisés avec succès. En ce qui concerne le Calix-COU-P, une forte exaltation de fluorescence et un déplacement bathochrome d'absorption ont été observés en présence de césium dans l'eau. Une très bonne limite de détection (0,77 μM) ainsi qu'une excellente sélectivité vis-à-vis du césium ont été observées, démontrant que Calix-COU-P pourrait être un capteur exceptionnel pour la détection de césium dans l'eau. Calix-COU-Benz-CN possède quant à lui des propriétés photophysiques prometteuses dans un milieu partiellement aqueux avec des bandes d'absorption et de fluorescence intenses en visible grâce à la présence des groupements benzothiazole et cyano. L'addition de césium conduit aux déplacements ver le bleu des spectres d'absorption et une augmentation de l'intensité de fluorescence. L'étude de la cinétique de complexation entre Calix-COU-Benz-CN et Cs+ par la technique « stopped-flow » a montré une cinétique rapide à faibles concentrations de cations et une cinétique plus longue à des concentrations élevées (> 10 mM). Calix-COU-Benz-CN a ensuite été incorporé dans un dispositif microfluidique. Une courbe d'étalonnage qui représente l'intensité de fluorescence en fonction de la concentration du césium montre une valeur de limite de détection de l’ordre de 2,0 μM. Deux composés analogues contenant la même entité complexante Calix[4]arène-couronne-6 ont été également synthétisés et greffés sur des nanoparticules magnétiques afin d’obtenir un matériau fonctionnalisé pour la décontamination de l’eau contenant le césium radioactif. L'étude préliminaire montre que les nanoparticules fonctionnalisées pourraient capter efficacement une quantité très faible du césium dans l’eau contaminée. Par la suite, en vue de développer des capteurs pour l’uranyle, une série de dérivés de salicylaldéhyde-azine ont été synthétisés et caractérisés. Leurs propriétés d'émission induites par l'agrégation (AIE) ont été étudiées. Dans un mélange eau/acétonitrile, les composés U1 et U2 présentent une forte fluorescence lors de l'agrégation tandis que le composé U3 ne présente pas cet effet AIE dans la même condition. Grâce aux sites de complexation contenant des atomes d’oxygène et d'azote, ces molécules présentent une complexation efficace avec les ions uranyle et induire une extinction de la fluorescence. Dans notre étude, il était intéressant de noter la présence d’uranyle conduit à une destruction de l'agrégation, en particulier pour la molécule U2 dans un mélange eau / acétonitrile 60:40. L’extinction de l’émission a été expliquée par des processus de destruction d'agrégats émissifs lors de la complexation avec le cation. Le mécanisme proposé a été validé par des expériences de diffusion dynamique de la lumière et de microscopie électronique à balayage. Le composé U2 présente une bonne sélectivité vis-à-vis de l'uranyle en présence des lanthanides et des autres cations compétitifs. Le capteur permet la détection de concentrations de l’ordre ppb en uranyle. Enfin, la synthèse et l'étude de nouveaux capteurs pour la détection de l’arsenic ont également été discutées. Une série de capteurs fluorescents portant l’entité complexante cystéine a été synthétisée et leurs propriétés complexantes pour l'arsenic ont été étudiées. De plus, des nanoparticules d'or modifiées par la cystéine, le glutathion et le dithiothréitol ont été synthétisées. La complexation de l'ion arsenic avec ces nanoparticules a été étudiée et discutée. Une perspective sur le développement de nouveaux capteurs pour l’arsenic a été proposée. / This thesis focuses on the synthesis, photophysical and complexation studies of fluorescent molecules for the selective detection of toxic cations such as cesium, uranyl and arsenic. Firstly, two new fluorescent sensors Calix-COU-P and Calix-COU-Benz-CN for cesium cations based on Calix[4]arene-crown-6 and coumarin fluorophore were successfully synthesized. For Calix-COU-P, a remarkable fluorescence enhancement and a red shift in absorption were observed due to the complexation with cesium cation in water. Good detection limits (0.77 µM) together with an excellent selectivity towards cesium were observed, demonstrating that Calix-COU-P could be an outstanding sensor for the detection of cesium cation in water. Calix-COU-Benz-CN possesses exceptional photophysical properties in an organoaqueous solution with intense visible absorption and emission bands thanks to benzothiazole and cyano groups. The addition of cesium cation to Calix-COU-Benz-CN offered noticeable blue shifts of the absorption spectra and considerably enhanced the emission intensity. The kinetic study of the complexation between Calix-COU-Benz-CN and Cs+ by stopped-flow experiments showed a rapid kinetic at small concentrations of cations and a lower kinetic at higher concentrations (> 10 mM). Calix-COU-Benz-CN was then incorporated into a microfluidic device. The voltage signals, which are proportional to the fluorescence intensity, were monitored continuously at various cesium concentrations. A calibration curve which represents the fluorescence intensity as a function of cesium cation concentration gives a value of detection limit up to 2.0 µM. This value is only slightly higher than the detection limit obtained by fluorescence titration (1.67 µM), which suggests that the microfluidic device is capable to provide good sensitivity towards targeted ion for real-world applications. Furthermore, two analogous compounds Calix-DOP and Calix-DOP-P containing the same complexing entity were also synthesized and grafted onto magnetic nanoparticles in order to obtain a functionalized material for the decontamination of the water containing radioactive cesium. The preliminary study shows that functionalized nanoparticles could efficiently sequester cesium ions from contaminated water.Afterward, to develop new sensors for the detection of uranyl cations, a series of salicylaldehyde azine derivatives have been synthesized and characterized. Their aggregation induced emission properties were studied. In water/acetonitrile solvent, compounds U1 and U2 exhibited strong fluorescence upon aggregation while compound U3 did not aggregate and stayed in solution as well-dispersed molecules. Owning to oxygen and nitrogen binding sites, the molecules could complex uranyl ions and induced fluorescence quenching. In our study, it was interesting to understand that the effect of uranyl was somewhat more destructive rather than constructive to the aggregation. The most obvious quenching effect was observed for the aggregates of U2 in water/acetonitrile 60:40. The emission quenching was explained by aggregate-breaking processes, that the emitting aggregates could be destroyed by the complexation with uranyl cation. The proposed mechanism was further supported by dynamic light scattering and scanning electron microscope experiments. Compound U2 showed good selectivity towards uranyl over lanthanides and other common cations. The sensor could detect uranyl up to ppb scale.Finally, synthesis and studies of new sensors for the detection of arsenic ion were also discussed. A series of fluorescent sensors bearing cysteine moiety was synthesized and their complexing properties for arsenic were studied. Furthermore, gold nanoparticles which were modified by cysteine, glutathione and dithiothreitol were synthesized. The complexation of arsenic ion with these modified gold nanoparticles was studied and discussed. A perspective for further development of arsenic sensors was proposed.

[pt] A calibração de padrões atômicos de tempo e freqüência, na forma atualmente realizada, apresenta o inconveniente de ter que se fazer o transporte do Padrão de Transferência até os laboratórios onde se encontram os padrões a serem calibrados. Isto se dá pelo fato destes laboratórios não possuírem uma maneira adequada para enviarem seus padrões ao Departamento do Serviço da Hora do Observatório Nacional (DSH/ON), órgão responsável perante o INMETRO na calibração em tempo e freqüência e detentor do Padrão Nacional. Propõe- se aqui a substituição do procedimento atual por um sistema de calibração automática via Internet, o que elimina a necessidade do deslocamento do Padrão de Transferência. Neste novo sistema de calibração, a referência passa a ser um receptor de GPS (Global Position Sistem), que assume o papel de Padrão de Transferência, ao qual o padrão a ser calibrado é ininterruptamente comparado. O acesso e armazenamento dos dados pelo DSH/ON é feito por meio de um programa que controla remotamente a calibração no laboratório via conexão pela Internet. O presente trabalho envolve uma comparação entre o sistema atual e o proposto aqui, todo o desenvolvimento e apresentação do programa computacional, a montagem de um sistema completo de simulação prática, inclusive com acesso remoto via Internet, a coleta e tratamento dos dados e a apresentação do procedimento utilizado para se chegar à incerteza de medição do sistema. Procura-se ressaltar a vantagem de um sistema de calibração automático, quanto à coleta dos dados, assim como a não dependência do transporte do Padrão de Transferência para a realização da calibração, evitando- se com isto a sua deterioração . Na conclusão deste trabalho a incerteza obtida é comparada com a do procedimento atualmente em prática e a partir desta comparação são feitas considerações quanto à implementação do novo sistema e ao uso do r eceptor de GPS como Padrão de Transferência. / [en] The time and frequency calibration of atomic standards presents the inconvenience of the need of transportation of the Transfer Standard to the laboratories in which stay the standards to be calibrate. This happens because the laboratories do not possess a way to send its standards to the Departamento do Serviço da Hora do Observatório Nacional (DSH/ON), organ representative of INMETRO in Time and Frequency calibrations and detainer of the National Standard. This work intends the substitution of the procedure adopted today by a system of automatic calibration using Internet, eliminating the need of the displacement of the Transfer Standard. In this new procedure, the reference is t he Global Position Sistem (GPS) receiver, assuming the role of the Transfer Standard, to which the standard to be calibrate is compared continuosly. The access and storage of the data for the DSH/ON are made by means of a computer code that remotely controls the calibration through an Internet connection. The present work involves a comparison among both systems, the whole development and presentation of the computer code, the assembling of a complete system of practical simulation, the acquisition and data treatment and the presentation of the procedure used to obtain the measurement of the uncertainty. The advantage of an automatic calibration system, as well as of the collection of the data, is the fact that it not depending of the transportation of the Reference Standard for the accomplishment of the calibratio. As a conclusion of this work the obtained uncertainty is compared with the one in use today and based in this comparison we made considerations about the implementation of the new system and the use of the GPS receiver as Transfer Standard. / [es] La calibración de padrones atómicos de tiempo y frecuencia, en la forma actualmente realizada, tiene el inconveniente de tener que realizar el transporte del Padrón de Transferencia hasta los laboratorios donde se encuentran los padrones que serán calibrados. Esto se debe al hecho de que estos laboratorios no poseen una manera adecuada para enviar sus padrones al Departamento de Servicio de la Hora del Observatorio Nacional (DSH/ON), óprgano responsable frente al INMETRO en la calibración en tiempo y frecuencia y detentor del Padrón Nacional. Se propone aqui la substituición del procedimiento actual por un sistema de calibración automática vía Internet, que elimina la necesidad del desplazamiento del Padrón de transferencia. En este nuevo sistema de calibración, la referencia pasa a ser un receptor de GPS (Global Position Sistem), que asume el papel de Padrón de Transferencia, al cual el padrón a ser calibrado es ininterruptamente comparado. El acceso y almacenamiento de los datos por el DSH/ON se realiza a través de un programa que controla remotamente la calibración en el laboratorio vía conexión por Internet. El presente trabajo compara el sistema actual con el aqui propuesto, todo el desarrollo y presenta el programa computacional, el montaje de un sistema completo de simulación práctica, incluso con acceso remoto víaa Internet, la recolección y tratamiento de datos y la presentación del procedimiento utilizado para llegar a los erros de medición del sistema. Se resalta la ventaja de un sistema de calibración automático, así como la no dependencia del transporte del Padrón de Transferencia para la realización de la calibración, evitando con esto su deterioración. En la conclusión de este trabajo se compara el error obtenido con el del procedimiento actualmente en práctica y a partir de esta comparación se realizan consideraciones respecto a la implementación del nuevo sistema y al uso del receptor de GPS como Padrón de Transferencia.

published_or_final_version / Geography and Geology / Doctoral / Doctor of Philosophy

The purpose of this experiment was to make positive assignment of the Cs133 energy levels excited by the inelastic scattering of neutrons.

Amongst treatment technologies, adsorption is rapidly gaining prominence because it can remove metal pollutants at low concentrations, economical, ease of operation, and the adsorbent can be regenerated for reuse. This study therefore, aimed at developing a simple material for selective removal of cesium from wastewater. An agricultural waste material (pine cone) was used as a cheap solid support for transition metal hexacyanoferrate and applied as biosorbents for cesium removal. The preparation and characterization of biosorbent for cesium removal in the presence of alkali metals is reported. The experimental procedure was carried out in three phases; the first phase described the sample preparation. Toluene-ethanol mixtures of different ratios were investigated as surface treatment method for pine cone and the optimum treatment ratio determined by measuring the improvement in surface properties of the pine cone such as bulk density, iodine number, and surface negative charge. The modification of pine cone with iron hexacyanoferrate was examined in the second phase. The preparation of potassium iron(III) hexacyanoferrate (KFeHCF) supported toluene-ethanol modified pine cone powder was studied in order to consider its application for cesium removal from aqueous solution. The biosorbent was designed to incorporate the hexacyanoferrate ligand which is known to have a high affinity for cesium ions in aqueous solution. Fe(III) was loaded onto the toluene-ethanol treated pine cone powder followed by hexacyanoferrate ligand incorporation on the biosorbent producing the potassium iron hexacyanoferrate supported toluene-ethanol treated pine cone. The modified pine cone was characterized by FTIR, XRD and TGA analysis. The influence of solution pH and adsorbent dose were studied. The application of potassium iron hexacyanoferrate for the selective removal of cesium in the presence of sodium and calcium was investigated in the third phase. Batch adsorption kinetic studies were performed to determine the effect of modification on cesium removal. Coefficient of correlation, r2, and Chi-square, χ2, methods were applied in the determination of the best fit kinetic method. Increasing the ratio of toluene in the extractant mixture increased formation of esters and iodine capacity of the material, but reduced carboxylate ions and surface charge. Maximum cesium vi adsorption was observed for the 2:1 toluene-ethanol treated sample. Structural characterization using FTIR, XRD and TGA confirmed the successful modification of KFeHCF pine cone powder. Cesium adsorption experiments indicate that KFeHCF supported toluene-ethanol modified pine was more efficient for cesium removal than the raw pine cone powder. Kinetic modeling of Cs+ adsorption was done using the pseudo-first, pseudo-second order and diffusion chemisorption kinetic models. The pseudo first order kinetics could not accurately predict the experimental data. The kinetics data fitted the pseudo-second order and diffusion-chemisorption models. The chemisorption diffusion model only accurately describes the experimental data after 5 min of contact whereas the pseudo second order describes the experimental data over the range of contact time. The application of the FeHCF modified pine cone for cesium removal from aqueous solution revealed that the FeHCF modified pine was less affected by the presence of competitive cations than the toluene-ethanol treated sample and the raw pine cone sample.

Nuclear plant stainless steel can become contaminated by radionuclides during normal operation whereby the final disposition of these materials then becomes a major decommissioning challenge to address. Characterisation of the chemical and metallurgical processes that underpin contamination is essential in consideration of developing cost effective decontamination and prevention methods, as are in situ measurement techniques that allow assessment of contamination. To address these issues, contamination experiments to simulate the nitric acid-based reprocessing streams of the PUREX (Plutonium Uranium Redox Extraction) process, and alkaline spent fuel storage ponds were investigated. Solution and surface spectroscopic measurements were performed to characterise the sorption behaviour of stable analogues of two high yield fission products, Sr-90 and Cs-137, on as received and 30 % cold rolled AISI Type 304 stainless steel, respectively. In addition Laser Induced Breakdown Spectroscopy (LIBS) was also investigated as a standoff contamination assessment technique. Fission product accumulation was modelled to a second order kinetic fit that considers chemisorption, typically to a hydrous metal oxide surface, as rate controlling. This process is observed to be independent of solution composition and strain processing regime. This behaviour reflects complexation to the passivating surface chromium oxide film, and as determined by depth elemental analysis, effectively inhibits contaminant migration into the bulk material. Environment chemistry and microstructural variables that destabilise the Cr-rich passive film however reduces the passive layer capabilities to effectively inhibit fission product bulk diffusion. The importance of corrosion phenomena towards radionuclide sorption processes necessitates the consideration of metallurgical and chemical factors during the implementation of decontamination approaches to treat affected plant material at nuclear licenced sites. LIBS was found to be a satisfactory technique for measurement of Sr sorbed to steel but Cs could not be detected at the concentrations used in this experimentation. Furthermore, EDX and TOF-SIMS elemental mapping indicated ablated material may be redistributed into the crater profile during elemental analysis. This process has clear implications for the deployment of LIBS for in situ characterisation of nuclear materials as the uncontrolled redistribution of radioactive material certainly violates decommissioning principles.