The work presented in this thesis is divided into two parts. The first part is the sorption of Ni and Eu to granitic materials, and cation exchange capacity measurements for powdered and intact samples. The second part is method development on autoradiography. In the first part, static batch sorption experiments were carried out to study the relative sorption properties of different granitic rocks and minerals. Experimental data were described using non-electrostatic correction models such as the Langmuir, Freundlich and Linear models. Sorption data obtained for sorption in a constant pH environment and variable metal concentration were used to test the Component Additive Model (CAM). Sorption test studies carried out using energy dispersive X-ray microanalysis were used to map the sorption of Eu on an intact sample. The results showed the CAM was applicable for Ni sorption to BG but that it was not applicable for Eu sorption to any of the granitic rocks studied. The sorption data fitted the CAM in the following order; BG (1) > GA (0.7) > RG (0.5) > GG (0.2), GrG (0.2) for Ni sorption and RG (0.7) > BG (0.4) > GA (0.2), GG (0.2), GrG (0.2) for Eu sorption to the different granitic rocks. Values in brackets represent the ratio of Rd-predicted/Rd-calculated. Results from the application of the CAM showed it was not possible to predict the Rd of the bulk sample from the component minerals. Desorption studies at constant pH were analysed by calculating the hysteresis H. The results showed that the higher the Rd the higher the hysteresis. Surface complexation using JChess Geochemical Code was used to obtain surface complexation parameters for the metal-solid complex for sorption in variable pH and constant metal concentration. Experimental data were described by the mass action law to obtained proton stoichiometry at which the sorption edge is defined. Results showed the presence of NaCl decreased the sorption of Ni, and increased the sorption of Eu. Sorption kinetics experiments in different carbonate complexing environments were carried out to study the effect of carbonate on Eu sorption capacity and rate of sorption. Data were fitted to first and second order kinetic models to investigate the sorption rates. Results showed the sorption to be fast initially before reaching a steady state after more than 200 hours of equilibration. Kinetic data confirmed the low sorption capacity observed for quartz. Data obtained for sorption in a mixed radionuclide system were modelled using the Linear model and the surface complexation model. The surface complexation constants are correlated to the Rd values obtained from the linear sorption isotherms. Modelling the results using Rdmix and Rdsing showed that sorption was suppressed in a mixed system, with no effect observed for sorption to feldspar in single and mixed systems. Cation exchange capacity (CEC) measurements were undertaken to deduce a correlation between the CEC of powdered rock samples and intact sample using rock beakers developed from the British Geological Survey by applying the Bascomb method in which the pH was buffered to pH 8.1. Normalising the results using the surface area showed that the CEC of the rock beakers was 6 orders of magnitude greater than that of the powdered sample. In the second part, a method for differentiating two or more radionuclides using storage phosphor imaging plates coupled with the Storm Scanner system was tested. Initial results showed that it is possible to differentiate one radionuclide from another in a mixed system using different levels of shielding.

No description available.

A interação de elementos potencialmente tóxicos com solos e a caracterização quanto à mobilidade e potencial de liberação ao ambiente são importantes para avaliação de risco ambiental. No caso de solos altamente intemperizados, como os Latossolos, a interação pode ser diferenciada devido à elevada acidez, baixa densidade de cargas negativas, maiores quantidades de minerais de argila 1:1 e de (hidr)óxidos de Fe, Al e Mn, em que predominam cargas negativas variáveis com o pH. O objetivo nesta tese foi caracterizar a capacidade de sorção, a distribuição entre as frações do solo, a especiação temporal, a predição da capacidade de sorção e a dessorção com método dinâmico de extração de Cd(II) em seis solos tropicais, incluindo três Latossolos. Amostras dos seis solos foram utilizadas para avaliação da interação com Cd(II), utilizando extração sequencial e especiação por espectroscopia de absorção de raios-X próximo à estrutura da borda (XANES) para avaliação da cinética de sorção. Dados de 29 solos foram utilizados para desenvolvimento de modelo de regressão linear para predição das capacidades de sorção de Cd(II). A caracterização da dessorção de Cd por extração convencional e dinâmica foi feita em solos de textura médio-arenosa, argilosa e em um solo de referência certificado. Os resultados de sorção foram ajustados ao modelo de Langmuir. As capacidades de sorção e as energias livres padrão de Gibbs variaram de 37 à 1296 mg kg-1 e de -16,6 até -27,0 kJ mol-1, respectivamente. A sorção foi fraca e reversível, e mais de 90% do Cd estava sorvido como espécies disponíveis. A especiação temporal indicou evidências fracas e variáveis para as alterações químicas do Cd no solo, sugerindo que o elemento liberado nessas amostras se ligou à matéria orgânica do solo e aos óxidos minerais ou permaneceu dissolvido, com pequenas alterações na especiação nos meses seguintes. O modelo linear representou 98% dos resultados empíricos apenas em função de uma variável, que foi o ensaio de sorção simplificado com apenas uma concentração de Cd(II). Apesar de a capacidade de sorção prevista com o modelo ter apresentado variação de cerca de 20% em relação ao empírico, o modelo de predição apresenta potencialidade de aplicação para avaliações iniciais e rápidas. A dessorção avaliada em batelada e em fluxo indicou dessorção próxima de 100% nas frações que representam disponibilidade no ambiente, enquanto o sistema desenvolvido para extração dinâmica foi adequado na mistura das soluções com a amostra de solo e propiciou rápida troca de extratores. De modo geral os atributos do solo, bem como a classe, influenciaram, mas não definiram a interação do Cd(II) com o solo. Por sua vez, o Cd(II) incorporado ao solo apresenta grande risco ambiental e de interação com a biota / The interaction of potentially toxic elements in soils and characterization as mobility and potential of environmental release are important for environmental risk assessment. In the case of highly weathered soils, as Oxisols, interaction can be differentiated, due to the high acidity, low density of negative charges, and higher amounts of 1:1 clay minerals and Fe, Al and Mn (hidr)oxides, in which negative charges are variables with pH. The objectives in this thesis was to characterize the Cd(II) sorption capacity, distribution between soil fractions, temporal speciation, prediction of sorption capacity and desorption with dynamic extraction method in six tropical soils, including three Oxisols. Samples of the six soils were used to assess the interaction with Cd(II) using sequential extraction and the speciation with X-ray absorption near edge structure spectroscopy (XANES) to evaluate the adsorption kinetics. Data of 29 soils were used to develop a linear regression model for prediction of Cd(II) sorption capacity. The Cd desorption characterization trough conventional and dynamics extractions was performed in a medium-sandy, a clayey and a certified reference soils. The sorption results were fitted to the Langmuir model. Sorption capacities and standard Gibbs free energy ranged from 37 to 1296 mg kg-1 and from -16.6 to -27.0 kJ mol-1, respectively. Sorption was weak and reversible, and more 90% Cd was sorbed as available species. The temporal speciation indicated weak and variables evidence of chemical changes of Cd in the soil, suggesting that this element released in these soils bound to the soil organic matter and to mineral oxides or remained dissolved, with minor changes in speciation in the following months. The linear model accounted for 98% of empirical results only on the basis of a single variable, which was the sorption simplified experiment with only one Cd(II) concentration. Although the sorption capacity predicted with the model ranged about 20% of the empirical, prediction model has potential of application for initial and rapid assessments. The desorption evaluated in batch and flow indicated desorption of about 100% in the fractions representing availability in the environment, meanwhile the system developed for dynamic extraction was adequate to mix the solutions with the soil sample and provided rapid exchange of extractants. Overall, the soil characteristics and the class had influence, but did not define the interaction of Cd(II) with the soil. On the other hand, the Cd(II) incorporated into the soil has a great environmental risk and to interact with the biota

Transport of amorphous and semi-crystalline, oriented, annealed and non-annealed PET films has been studied using pure and mixed gas/vapor feeds to understand the influence of flavor molecules on the efficacy of the barrier material. Methanol has been used as the flavor molecule simulant, and pure methanol vapor sorption studies show swelling and relaxation effects in the polymer. Multi-component transport of O2/methanol and O2/CO¬2/methanol mixtures, performed at different activities of methanol, shows that vapor induced plasticization leads to increases in O2 and CO2 permeability. Annealed, semi-crystalline PET is shown to be most resistant to plasticization effects. It has been shown that the non-annealed film is less stable despite similar crystallinity as the annealed film due to the presence of orientation related stress in the material. Presence of crystals also restricts the chain motion, and helps suppress the plasticization effects. The results have been compared with the predictions of the dual mode model for multi-component mixtures. Plasticization effects at the high activities have been analyzed within the framework of the free volume theory. It has been proposed that only the densified domains of a glassy polymer be considered when evaluating fractional free volume change due to swelling in the polymer-penetrant system. The free volume parameter- BA has been evaluated for O2 and CO2 in PET and is found to be different from that for other high permeability polymers.

A interação de elementos potencialmente tóxicos com solos e a caracterização quanto à mobilidade e potencial de liberação ao ambiente são importantes para avaliação de risco ambiental. No caso de solos altamente intemperizados, como os Latossolos, a interação pode ser diferenciada devido à elevada acidez, baixa densidade de cargas negativas, maiores quantidades de minerais de argila 1:1 e de (hidr)óxidos de Fe, Al e Mn, em que predominam cargas negativas variáveis com o pH. O objetivo nesta tese foi caracterizar a capacidade de sorção, a distribuição entre as frações do solo, a especiação temporal, a predição da capacidade de sorção e a dessorção com método dinâmico de extração de Cd(II) em seis solos tropicais, incluindo três Latossolos. Amostras dos seis solos foram utilizadas para avaliação da interação com Cd(II), utilizando extração sequencial e especiação por espectroscopia de absorção de raios-X próximo à estrutura da borda (XANES) para avaliação da cinética de sorção. Dados de 29 solos foram utilizados para desenvolvimento de modelo de regressão linear para predição das capacidades de sorção de Cd(II). A caracterização da dessorção de Cd por extração convencional e dinâmica foi feita em solos de textura médio-arenosa, argilosa e em um solo de referência certificado. Os resultados de sorção foram ajustados ao modelo de Langmuir. As capacidades de sorção e as energias livres padrão de Gibbs variaram de 37 à 1296 mg kg-1 e de -16,6 até -27,0 kJ mol-1, respectivamente. A sorção foi fraca e reversível, e mais de 90% do Cd estava sorvido como espécies disponíveis. A especiação temporal indicou evidências fracas e variáveis para as alterações químicas do Cd no solo, sugerindo que o elemento liberado nessas amostras se ligou à matéria orgânica do solo e aos óxidos minerais ou permaneceu dissolvido, com pequenas alterações na especiação nos meses seguintes. O modelo linear representou 98% dos resultados empíricos apenas em função de uma variável, que foi o ensaio de sorção simplificado com apenas uma concentração de Cd(II). Apesar de a capacidade de sorção prevista com o modelo ter apresentado variação de cerca de 20% em relação ao empírico, o modelo de predição apresenta potencialidade de aplicação para avaliações iniciais e rápidas. A dessorção avaliada em batelada e em fluxo indicou dessorção próxima de 100% nas frações que representam disponibilidade no ambiente, enquanto o sistema desenvolvido para extração dinâmica foi adequado na mistura das soluções com a amostra de solo e propiciou rápida troca de extratores. De modo geral os atributos do solo, bem como a classe, influenciaram, mas não definiram a interação do Cd(II) com o solo. Por sua vez, o Cd(II) incorporado ao solo apresenta grande risco ambiental e de interação com a biota / The interaction of potentially toxic elements in soils and characterization as mobility and potential of environmental release are important for environmental risk assessment. In the case of highly weathered soils, as Oxisols, interaction can be differentiated, due to the high acidity, low density of negative charges, and higher amounts of 1:1 clay minerals and Fe, Al and Mn (hidr)oxides, in which negative charges are variables with pH. The objectives in this thesis was to characterize the Cd(II) sorption capacity, distribution between soil fractions, temporal speciation, prediction of sorption capacity and desorption with dynamic extraction method in six tropical soils, including three Oxisols. Samples of the six soils were used to assess the interaction with Cd(II) using sequential extraction and the speciation with X-ray absorption near edge structure spectroscopy (XANES) to evaluate the adsorption kinetics. Data of 29 soils were used to develop a linear regression model for prediction of Cd(II) sorption capacity. The Cd desorption characterization trough conventional and dynamics extractions was performed in a medium-sandy, a clayey and a certified reference soils. The sorption results were fitted to the Langmuir model. Sorption capacities and standard Gibbs free energy ranged from 37 to 1296 mg kg-1 and from -16.6 to -27.0 kJ mol-1, respectively. Sorption was weak and reversible, and more 90% Cd was sorbed as available species. The temporal speciation indicated weak and variables evidence of chemical changes of Cd in the soil, suggesting that this element released in these soils bound to the soil organic matter and to mineral oxides or remained dissolved, with minor changes in speciation in the following months. The linear model accounted for 98% of empirical results only on the basis of a single variable, which was the sorption simplified experiment with only one Cd(II) concentration. Although the sorption capacity predicted with the model ranged about 20% of the empirical, prediction model has potential of application for initial and rapid assessments. The desorption evaluated in batch and flow indicated desorption of about 100% in the fractions representing availability in the environment, meanwhile the system developed for dynamic extraction was adequate to mix the solutions with the soil sample and provided rapid exchange of extractants. Overall, the soil characteristics and the class had influence, but did not define the interaction of Cd(II) with the soil. On the other hand, the Cd(II) incorporated into the soil has a great environmental risk and to interact with the biota

Made available in DSpace on 2014-12-17T15:42:26Z (GMT). No. of bitstreams: 1 WaldeniceAM.pdf: 1082421 bytes, checksum: bd7f6b4a35f59108d7807a3a68e163a3 (MD5) Previous issue date: 2007-03-27 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Textile activity results in effluents with a variety of dyes. Among the several processes for dye-uptaking from these wastewaters, sorption is one of the most effective methods, chitosan being a very promising alternative for this end. The sorption of Methyl Orange by chitosan crosslinked particles was approached using equilibrium and kinetic analyses at different pH s. Besides the standard pseudo-order analysis normally effectuated (i.e. pseudo-first-order and pseudo-second-order), a novel approach involving a pseudo-nth-order kinetics was used, nbeing determined via non-linear regression, using the Levenberg-Marquardt method. Zeta potential measurements indicated that electrostatic interactions were important for the sorption process. Regarding equilibrium experiments, data were well fitted to a hybrid Langmuir-Freundlich isotherm, and estimated Gibbs free energy of adsorption as a function of mass of dye per area of chitosan showed that the process of adsorption becomes more homogeneous as the pH of the continuous phase decreased. Considering the kinetics of sorption, although a pseudo-nth-order description yielded good fits, a kinetic equation involving diffusion adsorption phenomena was found to be more consistent in terms of a physicochemical description of the sorption process / A atividade t?xtil resulta em efluentes com uma variedade de corantes. Dentre os v?rios processos para a remo??o de corantes destes efluentes, o de sor??o constitui um dos m?todos mais efetivos, sendo a quitosana um sorvente alternativo bastante promissor para este fim. A sor??o do corante alaranjado de metila em part?culas de quitosana reticulada foi avaliada atrav?s de estudos de equil?brio e cin?tica de sor??o em diferentes pHs. Al?m da an?lise com o modelo de pseudo-ordem normalmente adotado na literatura (por exemplo, pseudo-primeira-ordem e pseudo-segunda-ordem), um novo modelo envolvendo uma cin?tica de pseudo-n-ordem foi usada, sendo ndeterminado via regress?o n?o-linear, usando o m?todo de Levenberg-Marquardt. Medidas de potencial zeta indicaram intera??es eletrost?ticas importantes no processo de sor??o. Com rela??o aos estudos de equil?brio, os dados foram bem representados pela isoterma h?brida Langmuir-Freundlich, e a energia livre de Gibbs de sor??o como uma fun??o da massa de corante por ?rea de part?cula mostrou que este processo torna-se mais homog?neo ? medida que o pH da fase cont?nua diminui. Considerando a cin?tica de sor??o, apesar do modelo de pseudo-n-ordem descrever bem os dados experimentais, a equa??o cin?tica envolvendo difus?o-adsor??o foi mais consistente em termos de descri??o f?sico-qu?mica do processo de sor??o

Made available in DSpace on 2014-12-17T15:41:57Z (GMT). No. of bitstreams: 1 RobertoRCL_DISSERT.pdf: 1216220 bytes, checksum: 291b5b64177a1fbc1bc254c50866a9c9 (MD5) Previous issue date: 2012-05-23 / The phenomenon of adsorption is of fundamental importance for the treatment of textile effluents and removal of dyes. Chitosan is characterized as an excellent adsorbent material, not only for its adsorption capacity but also the low cost production. Equilibrium and kinetic studies were developed in this study to describe the mechanism of adsorption of the anionic azo dye Orange G in chitosan, with the isotherms obtained from the variation of the concentration of dye in the continuous phase. The kinetics of the process was analyzed based on models involving the adsorption of molecules of the dye in nonpolar and polar sites. Adsorption experiments were carried out in water and in saline media with different NaCl concentrations, both for the determination of the equilibrium time as isotherms for making kinetic curves in which the amount of dye adsorbed measured indirectly varied with time. The experiments revealed the opening of the biopolymer structure with increasing concentration of Orange G, accompanied by high pH values and change on the type of interaction between the dye and the adsorbent surface, suggesting behavior advocated by the Langmuir equation in a certain range of concentration of the adsorbate and following the Henry's Law at higher concentrations, from the increased number of sites available for adsorption. The studies conducted showed that the saline medium reduces the chitosan s adsorption capacity according to a certain concentration, the occurrence of the cooperative adsorption process steps kinetic mechanism suggested as a new alternative for the interpretation of the phenomenon / O fen?meno da adsor??o ? de fundamental import?ncia no tratamento de efluentes t?xteis e remo??o de corantes. A quitosana caracteriza-se como excelente material adsorvente, n?o s? pela sua capacidade de adsor??o mas tamb?m pelo baixo custo de obten??o. Estudos cin?ticos e de equil?brio foram desenvolvidos neste trabalho para descrever o mecanismo de adsor??o do azo-corante ani?nico Alaranjado G em quitosana, com a obten??o de isotermas a partir da varia??o da concentra??o de corante na fase cont?nua. A cin?tica do processo foi analisada a partir de modelos envolvendo a adsor??o de mol?culas do corante em dois tipos de s?tios: polares e apolares. Experimentos de adsor??o foram desenvolvidos em ?gua e em meios salinos com diferentes concentra??es de NaCl, tanto para a determina??o do tempo de equil?brio como para a confec??o de isotermas e curvas cin?ticas nas quais a quantidade de corante adsorvido, medida de forma indireta, variou em fun??o do tempo. Os experimentos revelaram abertura da estrutura do biopol?mero com a eleva??o da concentra??o do Alaranjado G, acompanhada pela eleva??o do pH e modifica??o no tipo de intera??o entre o corante e a superf?cie do adsorvente, sugerindo comportamento preconizado pela equa??o de Langmuir em certa faixa de concentra??o do adsorvato e obedecendo ? lei de Henry em concentra??es mais elevadas, a partir do aumento do n?mero de s?tios dispon?veis para a adsor??o. Os estudos desenvolvidos mostraram que o meio salino reduz a capacidade de adsor??o do Alaranjado G em quitosana e pode impedir, em certa concentra??o, a ocorr?ncia de processo cooperativo de adsor??o conforme mecanismo cin?tico em etapas sugerido como uma nova alternativa para a interpreta??o do fen?meno

<p>Understanding of the processes affecting solute transport in flowing water is important for the possibility to predict the evolution with time of polluted stream systems. </p><p>This thesis presents tracer experiment methodology and model developments for solute transport in streams, with special focus on retention processes and their effect on solute stream transport. Results are presented from a tracer experiment in the Säva Stream, Uppland County, Sweden, where both a conservative (³H as tritiated water) and a reactive (⁵¹Cr as trivalent chromium ion) tracer were injected simultaneously. The time and length scales of the experiment were prolonged compared to previous studies, which allowed for new critical tests of different model concepts. </p><p>It was found that the hyporheic exchange greatly affected the solute transport of both tracers. However, the retention of chromium was significantly more pronounced. About 76% of the injected chromium was lost from the stream water phase directly after the passage of the pulse 30 km downstream of the injection point. The inventory of chromium in the sediments indicated that the main part was retrieved in the hyporheic zone. </p><p>Both a diffusive and an advective hyporheic exchange model were developed and evaluated versus independent observations in the stream water and hyporheic zone. Analytical expressions for the central temporal moments of the breakthrough curve and semi-analytical solutions for the solute concentration in the Laplace domain were derived. Both models were found useful in representing the observations.</p><p>For the transport of the reactive solute, it was found essential to consider a kinetic sorption on to particulate matter in the hyporheic zone. The time needed for a wash-out of 75% of the maximum uptake in the hyporheic zone was found to be ~85 times longer for the reactive solute, compared to the conservative solute. Neglecting the sorption kinetics in the transport model yielded significant errors in the central temporal moments, which implied an incorrect description of the wash-out process from the hyporheic zone. Independent observations in the stream water and hyporheic zone as well as choice of evaluation method are essential for a correct interpretation of the processes.</p><p>A first attempt was also made to link model parameters such as the residence time in the hyporheic zone with measurable parameters of the stream. Such a relationship offers the possibility to generalize results for other streams and stream conditions. A generic study of the transport of an inert solute in the Lule River, Sweden, using this kind of relationship, indicated that the hyporheic exchange can have a large practical implication.</p>

<p>The overall objective of the current study is to develop a quantitative understanding of the effects of spatial variability in physical and geochemical properties of crystalline rock on the migration of radionuclides along a single fracture in bedrock. A stochastic model was developed to describe the transport of solutes in fractured rock. The model describes the migration of radionuclides along a one-dimensional path and includes the transversal diffusion into the rock matrix and sorption kinetics. By using a Lagrangian method of description we can extend the model to the description of a two-dimensional transport problem in single fractures. </p><p>This study presents the first analysis of the impact of heterogeneous mass transfer on the transport of radionuclides in rock fractures, where most of the relevant rock properties such as aperture, porosity, effective diffusivity, sorption capacity and maximum diffusion depth are defined as being spatially random. The stochastic analysis performed here reflects the uncertainty in our knowledge of the properties associated with a discrete sampling technique in site investigations.</p><p>Geostatistics of the main parameters was determined experimentally on a large number of rock samples taken from the Swedish crystalline basement. The knowledge of the covariance functions of the main rock properties is then used as a basis for a stochastic analysis. By combining the small perturbation approach with the spectral method the problem could be solved in terms of closed form solutions for the central temporal moments of the residence time probability density function. </p><p>In order to be able to distinguish between the effects of various mechanisms from the effects of heterogeneity on the migration of radionuclides, it was necessary to perform independent studies of the effect of the variation of the dispersion coefficient on the aspect ratio of a rectangular flow section and the effect of adsorption kinetics on the migration. </p><p>Finally, the effect of the heterogeneous rock properties on the solute transport observed in a limited number of migration experiments corresponds fairly well to the theoretical effect expected on the basis of the experimentally determined auto-covariance functions. </p>

The overall objective of the current study is to develop a quantitative understanding of the effects of spatial variability in physical and geochemical properties of crystalline rock on the migration of radionuclides along a single fracture in bedrock. A stochastic model was developed to describe the transport of solutes in fractured rock. The model describes the migration of radionuclides along a one-dimensional path and includes the transversal diffusion into the rock matrix and sorption kinetics. By using a Lagrangian method of description we can extend the model to the description of a two-dimensional transport problem in single fractures. This study presents the first analysis of the impact of heterogeneous mass transfer on the transport of radionuclides in rock fractures, where most of the relevant rock properties such as aperture, porosity, effective diffusivity, sorption capacity and maximum diffusion depth are defined as being spatially random. The stochastic analysis performed here reflects the uncertainty in our knowledge of the properties associated with a discrete sampling technique in site investigations. Geostatistics of the main parameters was determined experimentally on a large number of rock samples taken from the Swedish crystalline basement. The knowledge of the covariance functions of the main rock properties is then used as a basis for a stochastic analysis. By combining the small perturbation approach with the spectral method the problem could be solved in terms of closed form solutions for the central temporal moments of the residence time probability density function. In order to be able to distinguish between the effects of various mechanisms from the effects of heterogeneity on the migration of radionuclides, it was necessary to perform independent studies of the effect of the variation of the dispersion coefficient on the aspect ratio of a rectangular flow section and the effect of adsorption kinetics on the migration. Finally, the effect of the heterogeneous rock properties on the solute transport observed in a limited number of migration experiments corresponds fairly well to the theoretical effect expected on the basis of the experimentally determined auto-covariance functions.