Typescript. Includes vita and abstract. Bibliography: Includes bibliographical references (leaves 62-69). Description: viii, 68 leaves : ill. ; 29 cm.

O presente estudo objetivou a caracterização hidrogeoquímica da microbacia de drenagem Entre Rios, reflorestada com eucaliptos utilizando-se modelos de transporte de materiais nas fases dissolvidas e particuladas, em períodos de amostragens, antes e depois da realização da colheita de madeira. Na área experimental foram coletadas amostras de águas fluviais, material particulado em suspensão, águas de chuva, solos e sedimentos de fundo. Foram determinados importantes parâmetros e variáveis como vazão, concentração de íons majoritários e material particulado em suspensão, variabilidade temporal e transportes de material dissolvido e particulado, mecanismos de aporte difuso e pontual da carga dissolvida, separação das componentes superficial e subterrânea no escoamento total, concentração e biodisponibilidade dos principais metais pesados nos solos e sedimentos de fundo do córrego. As características hidroquímicas das águas fluviais mostraram que as espécies químicas SiO2, HCO3 -, Ca2+, Mg2+ e Na+ apresentaram comportamentos de diluição com o aumento da vazão e aportes de origem difusa, em todo período, relacionadas à formação geológica da região e mecanismos de recarga da bacia. A amostragem realizada cinco meses após a colheita de madeira evidenciou anomalias de K+ e Cl- que apresentaram padrões de aumento de suas concentrações em relação ao aumento das respectivas vazões, associadas à aplicação de insumos agrícolas. O transporte específico de TDS na amostragem anterior à colheita foi de 35,81 kg km-2d-1, e posterior à colheita foi de 23,53 kg km-2d-1 pelo método estocástico. Tal transporte foi composto principalmente de SiO2 e HCO3 - e a origem destas espécies estiveram associadas à alterações de rochas e aportes atmosféricos totais. Em termos de MPS, as concentrações obtidas se relacionaram positivamente com a vazão nas amostragens intensivas indicando maiores arrastes deste material nas maiores vazões, com concentrações máximas de 50,2 e 80,6 mg L-1 antes e após a colheita, respectivamente. A erosão mecânica da microbacia mostrou-se com uma taxa de degradação física dos solos de 8,7 m Ma-1.Em relação aos aportes atmosféricos, as espécies químicas mais representativas foram o Ca2+ e o Na+ para os cátions e HCO3 -, NO3 - e SO4 2- para os ânions. O transporte específico do TDS nas águas de chuva foi de 4,10 t km-2 a-1. Pelas razões dos transportes totais de águas pluviais e fluviais ficou evidenciado um controle dos aportes atmosféricos totais sobre as águas do córrego da microbacia. Cr, Cd, Co, Cu, Zn e Sc foram os metais pesados com maiores concentrações no solo LVd da microbacia. A especiação química dos solos revelou que o LVd foi solo que apresentou maior fração biodisponível para Cd e Zn e estiveram associados principalmente as frações óxidos de ferro cristalino e matéria orgânica, respectivamente. Os resultados dos fatores de enriquecimento para as camadas de 0-10 cm dos solos da microbacia de drenagem não evidenciaram influência antrópica causada pelos tratos culturais, exceto pelo Cu no solo LVAd na camada de 0-10 cm / This study aimed to characterize the Entre Rios stream small watershed hydrogeochemistry, reforested with eucalyptus using materials transport models in dissolved and particulate phases, in periods of sampling, before and after the clearcutting. In the experimental area were collected river water samples, suspended particulate material, rain water, soil and botton sediments. Were determined important parameters and variables such as discharge, major íons concentration, and suspended particulate material, temporal variability and dissolved and particulate transports, punctual and diffuse input mechanisms of the dissolved load, superficial and sub superficial components of the total discharge, concentration and bioavailability of the major heavy metals in soils and bottoms sediments. Hydrochemistry characteristics of the fluvial waters showed that chemical species SiO2, HCO3 -, Ca2+, Mg2+ and Na+ presented dilution behavior with increasing of the discharge and diffuse input, in any period, related to the regional geological formation and watershed recharge mechanisms. Sampling performed five months after the clearcutting showed abnormalities of K+ and Clthat showed increase of their concentrations with the discharge, associated with the agricultural inputs application. The TDS specific transport in the sample before clearcutting was 35.81 kg km-2d-1, and after was 23.53 kg km-2d-1 calculated by the stochastic method. This transport was composed mainly of the SiO2 and HCO3 - and the origin of these species were associated with rock alterations and total atmospheric inputs. In terms of MPS, the concentrations were related positively with the discharge in intensive sampling indicating more haul of this material in the higher discharge with maximum concentrations of the 50.2 and 80.6 mg L-1 before and after clearcutting, respectively. The mechanical erosion showed a soil physical degradation tax of the 8.7 m Ma-1. In relation of atmospherics inputs, the most representative chemical species were Ca2+ and Na+ and HCO3 -, NO3 -, SO4 2-. The TDS specific transport in rain waters was 4.10 t km-2 y-1. The rations between rainwater and river transports demonstrated the control of the atmospheric total contributions in the watershed waters. Cr, Cd, Co, Cu, Zn and Sc were heavy metals with higher concentrations LVd in soil. The soils chemical speciation showed to the LVd soil higher bioavailable fraction for Cd and Zn and were associated mainly with crystalline iron oxides and organic matter, respectively. The enrichment factors results for the 0-10 cm soil layer in the watershed showed no anthropogenic influence caused by cultural treatments, except for the Cu in 0-10 cm LVAd soil layer

O presente estudo objetivou a caracterização hidrogeoquímica da microbacia de drenagem Entre Rios, reflorestada com eucaliptos utilizando-se modelos de transporte de materiais nas fases dissolvidas e particuladas, em períodos de amostragens, antes e depois da realização da colheita de madeira. Na área experimental foram coletadas amostras de águas fluviais, material particulado em suspensão, águas de chuva, solos e sedimentos de fundo. Foram determinados importantes parâmetros e variáveis como vazão, concentração de íons majoritários e material particulado em suspensão, variabilidade temporal e transportes de material dissolvido e particulado, mecanismos de aporte difuso e pontual da carga dissolvida, separação das componentes superficial e subterrânea no escoamento total, concentração e biodisponibilidade dos principais metais pesados nos solos e sedimentos de fundo do córrego. As características hidroquímicas das águas fluviais mostraram que as espécies químicas SiO2, HCO3 -, Ca2+, Mg2+ e Na+ apresentaram comportamentos de diluição com o aumento da vazão e aportes de origem difusa, em todo período, relacionadas à formação geológica da região e mecanismos de recarga da bacia. A amostragem realizada cinco meses após a colheita de madeira evidenciou anomalias de K+ e Cl- que apresentaram padrões de aumento de suas concentrações em relação ao aumento das respectivas vazões, associadas à aplicação de insumos agrícolas. O transporte específico de TDS na amostragem anterior à colheita foi de 35,81 kg km-2d-1, e posterior à colheita foi de 23,53 kg km-2d-1 pelo método estocástico. Tal transporte foi composto principalmente de SiO2 e HCO3 - e a origem destas espécies estiveram associadas à alterações de rochas e aportes atmosféricos totais. Em termos de MPS, as concentrações obtidas se relacionaram positivamente com a vazão nas amostragens intensivas indicando maiores arrastes deste material nas maiores vazões, com concentrações máximas de 50,2 e 80,6 mg L-1 antes e após a colheita, respectivamente. A erosão mecânica da microbacia mostrou-se com uma taxa de degradação física dos solos de 8,7 m Ma-1.Em relação aos aportes atmosféricos, as espécies químicas mais representativas foram o Ca2+ e o Na+ para os cátions e HCO3 -, NO3 - e SO4 2- para os ânions. O transporte específico do TDS nas águas de chuva foi de 4,10 t km-2 a-1. Pelas razões dos transportes totais de águas pluviais e fluviais ficou evidenciado um controle dos aportes atmosféricos totais sobre as águas do córrego da microbacia. Cr, Cd, Co, Cu, Zn e Sc foram os metais pesados com maiores concentrações no solo LVd da microbacia. A especiação química dos solos revelou que o LVd foi solo que apresentou maior fração biodisponível para Cd e Zn e estiveram associados principalmente as frações óxidos de ferro cristalino e matéria orgânica, respectivamente. Os resultados dos fatores de enriquecimento para as camadas de 0-10 cm dos solos da microbacia de drenagem não evidenciaram influência antrópica causada pelos tratos culturais, exceto pelo Cu no solo LVAd na camada de 0-10 cm / This study aimed to characterize the Entre Rios stream small watershed hydrogeochemistry, reforested with eucalyptus using materials transport models in dissolved and particulate phases, in periods of sampling, before and after the clearcutting. In the experimental area were collected river water samples, suspended particulate material, rain water, soil and botton sediments. Were determined important parameters and variables such as discharge, major íons concentration, and suspended particulate material, temporal variability and dissolved and particulate transports, punctual and diffuse input mechanisms of the dissolved load, superficial and sub superficial components of the total discharge, concentration and bioavailability of the major heavy metals in soils and bottoms sediments. Hydrochemistry characteristics of the fluvial waters showed that chemical species SiO2, HCO3 -, Ca2+, Mg2+ and Na+ presented dilution behavior with increasing of the discharge and diffuse input, in any period, related to the regional geological formation and watershed recharge mechanisms. Sampling performed five months after the clearcutting showed abnormalities of K+ and Clthat showed increase of their concentrations with the discharge, associated with the agricultural inputs application. The TDS specific transport in the sample before clearcutting was 35.81 kg km-2d-1, and after was 23.53 kg km-2d-1 calculated by the stochastic method. This transport was composed mainly of the SiO2 and HCO3 - and the origin of these species were associated with rock alterations and total atmospheric inputs. In terms of MPS, the concentrations were related positively with the discharge in intensive sampling indicating more haul of this material in the higher discharge with maximum concentrations of the 50.2 and 80.6 mg L-1 before and after clearcutting, respectively. The mechanical erosion showed a soil physical degradation tax of the 8.7 m Ma-1. In relation of atmospherics inputs, the most representative chemical species were Ca2+ and Na+ and HCO3 -, NO3 -, SO4 2-. The TDS specific transport in rain waters was 4.10 t km-2 y-1. The rations between rainwater and river transports demonstrated the control of the atmospheric total contributions in the watershed waters. Cr, Cd, Co, Cu, Zn and Sc were heavy metals with higher concentrations LVd in soil. The soils chemical speciation showed to the LVd soil higher bioavailable fraction for Cd and Zn and were associated mainly with crystalline iron oxides and organic matter, respectively. The enrichment factors results for the 0-10 cm soil layer in the watershed showed no anthropogenic influence caused by cultural treatments, except for the Cu in 0-10 cm LVAd soil layer

Contaminant release and transport in platinum tailings are poorly studied in literature. This study serves to characterise these processes. The tailings facility is located in Steelpoort, Mpumalanga, South Africa on Critical Zone rocks of the Rustenburg Layered Suite in The Bushveld Igneous Complex. Tailings material samples were collected by hand auger- and direct push probe drilling at specific locations to represent the different materials present in the tailings facility. Water samples were collected from monitoring boreholes as well as the Steelpoort River. The samples were analysed using XRD, XRF, ABA, NAG, Reflected Light Microscopy, Acid Leaching Tests and ICP scans. Using the collected data, a geochemical model was constructed for the interpretation of mineral phase dissolution and to trace the mineral phases releasing contaminants. Analysis-, test- and modelling results showed that alteration mineral phases formed within ten years in the tailings material and that the existing alteration phases viz. talc and chlorite, as well as sulphides, are the major contributors of contaminants. Elevated pH values as well as major cation and anion concentrations were found in the fluid discharging from the tailings as well as the in groundwater, with little to no heavy metals, which were traced directly to the chromite phase. This suggests that platinum tailings do not contribute to heavy metal contamination or acid rock drainage but may increase aquifer salinity and alkalinity. The flow through the tailings, underlying vadose zone and fractured rock aquifer was characterised using permeameter- and pumping tests. From the data collected, an unsaturated flow model was developed to characterise the flow through the tailings. From the model, discharge from the tailings was calculated to take place at 0.7m per decade into the underlying vadose zone with fracture flow in the aquifer ranging from 0.46-0.026m/d, as calculated from pumping test results. Contaminant migration into the Steelpoort River is possibly inhibited by the Dwarsriver Fault, based on the chemical data and hydraulic conductivities calculated. Therefore, groundwater is considered to be the major receptor in the system and groundwater users may be negatively impacted by increasing groundwater salinity and major ion concentrations. / Dissertation (MSc)--University of Pretoria, 2013. / Geology / unrestricted

Reservoir heterogeneities exhibit a wide range of length scales, and their interaction with various transport mechanisms control the overall performance of subsurface flow and transport processes. Modeling these processes at large-scales requires proper scale-up of both heterogeneity and the underlying transport mechanisms. This research demonstrates a new reservoir modeling procedure to systematically quantify the scaling characteristics of transport processes by accounting for sub-scale heterogeneities and their interaction with various transport mechanisms based on the volume averaging approach. Although treatments of transport problems with the volume averaging technique have been published in the past, application to real geological systems exhibiting complex heterogeneity is lacking. A novel procedure, where results from a fine-scale numerical flow simulation reflecting the full physics of the transport process albeit over a small sub-volume of the reservoir, can be integrated with the volume averaging technique to provide effective description of transport at the coarse scale. In a volume averaging procedure, scaled up equations describing solute transport in single-phase flow are developed. Scaling characteristics of effective transport coefficient corresponding to different reservoir heterogeneity correlation lengths as well as different transport mechanisms including convection, dispersion, and diffusion are studied. The method is subsequently extended to describe transport in multiphase systems to study scaling characteristics of processes involving adsorption and inter-phase transport. Key conclusions drawn from this dissertation show that 1) variance of reservoir properties and flow responses generally decrease with scale; 2) scaling of recovery processes can be described by the scaling of effective mass transfer coefficient (Keff); in particular, mean and variance of Keff decrease with length scale, similar in the fashion of recovery statistics (e.g., variances in tracer breakthrough time and recovery); 3) the scaling of Keff depends on the underlying heterogeneity and is influenced by the dominant transport mechanisms. To show the versatility of the approach for studying scale-up of other transport mechanisms, it is also applied to derive scaled up formulations of non-Newtonian polymer flow to investigate the scaling characteristics of the apparent viscosity and effective shear rate in porous media. / text

A caracterização hidrogeoquímica da bacia do rio Sorocaba foi realizada a partir do estudo detalhado das cargas fluviais particulada e dissolvida, considerando a dinâmica dos transportes das principais espécies químicas, bem como os aportes atmosféricos e antrópicos, identificando os processos erosivos mecânicos e químicos predominantes na bacia de drenagem. A caracterização hidrológica permitiu identificar os principais mecanismos de recarga e descarga na bacia de drenagem e determinar o escoamento superficial rápido, revelando os períodos de maior potencial erosivo nos últimos 20 anos. O estudo da dinâmica da carga fluvial particulada mostrou a ocorrência de processos de remobilização e sedimentação ao longo da bacia, permitindo verificar um aumento do transporte fluvial específico em 2,5 vezes das nascentes até a foz. A erosão mecânica, calculada com base no transporte de sedimentos finos em suspensão junto à foz do rio Sorocaba, foi de 55,70 t km-2 a-1, indicando uma taxa de degradação física de 37,88 m Ma-1. A origem da matéria orgânica na carga particulada fluvial se mostrou associada aos efluentes domésticos após caracterização isotópica do 13C. O comportamento hidroquímico fluvial evidenciou uma diferença de predomínio de espécies químicas dissolvidas entre as cinco estações de amostragem, permitindo verificar a influência dos processos de diluição fluvial, de acordo com as relações concentração x vazão. O modelo geoquímico utilizado permitiu estimar o CO2 atmosférico/solo consumido durante o processo de alteração de rochas na bacia de drenagem em 198 x 103 moles km-2 a-1, dos quais 98% foi relacionado à alteração de silicatos. O modelo de reconstituição desse consumo nos últimos 59 anos mostrou-se pouco variável, entretanto o modelo associado exclusivamente aos silicatos indicou um aumento no mesmo período, a uma taxa de 2,7 x103 moles km-2 a-1. Comparada com a erosão mecânica, a erosão química se mostrou inferior em cerca de 2,5 vezes, enquanto que, ainda em termos de erosão química, as taxas de alteração de silicatos e carbonatos na bacia de drenagem foram de 9,4 e 5,3 m Ma-1, respectivamente. O índice de alteração de rocha RE, determinado a partir dos dados geoquímicos das águas fluviais, indicou a mudança de um possível domínio de estabilidade da caulinita para o das argilas 2:1, evidenciando a ocorrência do processo de bisialitização / The hydrogeochemical characterization of the Sorocaba River basin was performed from the detailed study of particulate and dissolved river loads. Considering the main chemical species transported, as well as the atmospheric and anthropogenic inputs, it ws identified the mechanical and chemical erosion processes prevailing in the drainage basin. The hydrologic characterization identified the main mechanisms of recharge and discharge in the drainage basin, and allowed to determine the quickly surface runoff, showing periods of increased erosion potential in the last 20 years. The study of the particulate load dynamics demonstrated the occurrence of sedimentation and remobilization processes in the basin, allowing to verify a specific fluvial transport increased by 2.5 times from headwaters to the mouth of the Sorocaba River. The mechanical erosion, calculated based on the fine suspended sediments transported at the mouth of the Sorocaba River, was 55.70 t km-2 yr-1, indicating a physical degradation rate of 37.88 m Myr-1. The origin of organic matter present in the particulate load was associated to domestic sewage, after isotopic characterization of the 13C. The fluvial hydrochemical performance revealed the predominance of different dissolved chemical species between the five sampling stations, enabling to verify the influence of fluvial dilution processes, according to the concentration-discharge relationships. The geochemical model used allowed us to estimate CO2 atmospheric / soil consumed during the alteration rocks process in the drainage basin of 198 x 103 mol-1 km2 yr-1, which 98% was related to silicates alteration. The reconstitution model of this consumption in the last 59 years has shown to be little variable, however the model exclusively associated with silicates demonstrated an increase during same period, in a rate of 2.7 x 103 moles km-2 yr-1. Compared to mechanical erosion, the chemical erosion was inferior to about 2.5 times, whereas, also in terms of chemical erosion, the silicate and carbonate alterations rates in the drainage basin were 9.4 and 5.3 m Myr-1, respectively. The rock alteration index RE, determined from the geochemical data, indicated a possible change in the kaolinite stability domain to the clays 2:1, indicating the occurrence of the bisialitization process

O objetivo do presente trabalho foi o estudo e analises de processos de transferência de energia e transferência de elétrons em dispositivos moleculares. Para tal fim foi utilizado o polímero de poliestireno (PS) como matriz hospedeira das moléculas tendo sido verificado que este material apresenta uma característica de um excelente isolante mostrando-se adequado para a fabricação de dispositivos moleculares do tipo elétrico e óptico. Os dispositivos moleculares ópticos e elétricos foram obtidos pela técnica de \"spin coating\" a partir de soluções contendo o polímero de PS e as moléculas de Alq3 e Rh590 em solvente orgânico, mostrando que esta técnica permite a obtenção de filmes com espessura de 200nm e rugosidade com RMS da ordem de 2nm. Foi verificado que filmes de PS contendo moléculas de Alq3 e Rh590 podem ser utilizadas como dispositivos de transferência de energia e que a eficiência de transferência depende da sobreposição da banda de emissão do Alq3, banda de absorção da Rh590 e a concentração relativa das moléculas; tendo sido obtido dispositivos com ate 86 % de eficiência de transferência. Foi verificado que os dispositivos de ITO/PS:Alq3/Al e ITO/PS:Alq3:Rh590/Al apresentam mecanismos de transporte do tipo de transporte limitado por cargas armadilhadas nos níveis de defeito situadas na região da banda proibida entre o HOMO e LUMO das moléculas de Alq3 e Rh590. Os dispositivos elétricos de ITO/PS:Alq3/Al mostraram a existência de efeito memória que foram atribuídos a mudanças nos estados de ocupação de níveis altamente localizados (armadilhas) e à existência de nano- partículas metálicas no interior do filme de PS:Alq3 promovendo a transferência de elétrons por efeitos de tunelamento ressonante. Os resultados obtidos no presente trabalho em relação aos mecanismos de transferência de energia e eletrônica apresentam-se promissores para futuras aplicações em dispositivos moleculares como memórias moleculares, chaves moleculares, dispositivos de emissão (OLEDs). / The aim of the present work was to study and analyses the energy and electron transfer process in molecular devices. The molecular devices were fabricated by using the polystyrene polymer because this material, as it was verified in this work, showed a good insulator features. The optical and electrical molecular devices were fabricated by using the spin-coating techniques from the PS, Alq3 and Rh520 solution in organic solvent. The thin film obtained by this technique showed a 200 nm of thickness and 2 nm RMS of roughness, that it is a good parameter values in order to obtain a molecular devices. The thin film of PS with Alq3 and Rh520 as host molecules acts as a good energy transfer device yielding the transfer efficiency of 86%. The transfer efficiency showed dependence on relative concentration of molecules in the PS film and in the good emission an absorption spectra overlapping of molecules. The molecular device of type ITO/PS:Alq3/Al and ITO/PS:Alq3:Rh520/Al used as molecular device of electrical type showed that the electrons transfer mechanism is limited by charge trapped in the localized level between HOMO and LUMO levels of the molecules. The devices of the type ITO/PS:Alq3/Al showed additionally a memory and negative resistance features that it was attributed to the change in the charge trapped levels due to device polarization and to the existence of Al nano particles into the PS film. The results obtained in this work showed high cientific and technological relevance in order to project and fabricate the molecular devices.

A caracterização hidrogeoquímica da bacia do rio Sorocaba foi realizada a partir do estudo detalhado das cargas fluviais particulada e dissolvida, considerando a dinâmica dos transportes das principais espécies químicas, bem como os aportes atmosféricos e antrópicos, identificando os processos erosivos mecânicos e químicos predominantes na bacia de drenagem. A caracterização hidrológica permitiu identificar os principais mecanismos de recarga e descarga na bacia de drenagem e determinar o escoamento superficial rápido, revelando os períodos de maior potencial erosivo nos últimos 20 anos. O estudo da dinâmica da carga fluvial particulada mostrou a ocorrência de processos de remobilização e sedimentação ao longo da bacia, permitindo verificar um aumento do transporte fluvial específico em 2,5 vezes das nascentes até a foz. A erosão mecânica, calculada com base no transporte de sedimentos finos em suspensão junto à foz do rio Sorocaba, foi de 55,70 t km-2 a-1, indicando uma taxa de degradação física de 37,88 m Ma-1. A origem da matéria orgânica na carga particulada fluvial se mostrou associada aos efluentes domésticos após caracterização isotópica do 13C. O comportamento hidroquímico fluvial evidenciou uma diferença de predomínio de espécies químicas dissolvidas entre as cinco estações de amostragem, permitindo verificar a influência dos processos de diluição fluvial, de acordo com as relações concentração x vazão. O modelo geoquímico utilizado permitiu estimar o CO2 atmosférico/solo consumido durante o processo de alteração de rochas na bacia de drenagem em 198 x 103 moles km-2 a-1, dos quais 98% foi relacionado à alteração de silicatos. O modelo de reconstituição desse consumo nos últimos 59 anos mostrou-se pouco variável, entretanto o modelo associado exclusivamente aos silicatos indicou um aumento no mesmo período, a uma taxa de 2,7 x103 moles km-2 a-1. Comparada com a erosão mecânica, a erosão química se mostrou inferior em cerca de 2,5 vezes, enquanto que, ainda em termos de erosão química, as taxas de alteração de silicatos e carbonatos na bacia de drenagem foram de 9,4 e 5,3 m Ma-1, respectivamente. O índice de alteração de rocha RE, determinado a partir dos dados geoquímicos das águas fluviais, indicou a mudança de um possível domínio de estabilidade da caulinita para o das argilas 2:1, evidenciando a ocorrência do processo de bisialitização / The hydrogeochemical characterization of the Sorocaba River basin was performed from the detailed study of particulate and dissolved river loads. Considering the main chemical species transported, as well as the atmospheric and anthropogenic inputs, it ws identified the mechanical and chemical erosion processes prevailing in the drainage basin. The hydrologic characterization identified the main mechanisms of recharge and discharge in the drainage basin, and allowed to determine the quickly surface runoff, showing periods of increased erosion potential in the last 20 years. The study of the particulate load dynamics demonstrated the occurrence of sedimentation and remobilization processes in the basin, allowing to verify a specific fluvial transport increased by 2.5 times from headwaters to the mouth of the Sorocaba River. The mechanical erosion, calculated based on the fine suspended sediments transported at the mouth of the Sorocaba River, was 55.70 t km-2 yr-1, indicating a physical degradation rate of 37.88 m Myr-1. The origin of organic matter present in the particulate load was associated to domestic sewage, after isotopic characterization of the 13C. The fluvial hydrochemical performance revealed the predominance of different dissolved chemical species between the five sampling stations, enabling to verify the influence of fluvial dilution processes, according to the concentration-discharge relationships. The geochemical model used allowed us to estimate CO2 atmospheric / soil consumed during the alteration rocks process in the drainage basin of 198 x 103 mol-1 km2 yr-1, which 98% was related to silicates alteration. The reconstitution model of this consumption in the last 59 years has shown to be little variable, however the model exclusively associated with silicates demonstrated an increase during same period, in a rate of 2.7 x 103 moles km-2 yr-1. Compared to mechanical erosion, the chemical erosion was inferior to about 2.5 times, whereas, also in terms of chemical erosion, the silicate and carbonate alterations rates in the drainage basin were 9.4 and 5.3 m Myr-1, respectively. The rock alteration index RE, determined from the geochemical data, indicated a possible change in the kaolinite stability domain to the clays 2:1, indicating the occurrence of the bisialitization process

O objetivo do presente trabalho foi o estudo e analises de processos de transferência de energia e transferência de elétrons em dispositivos moleculares. Para tal fim foi utilizado o polímero de poliestireno (PS) como matriz hospedeira das moléculas tendo sido verificado que este material apresenta uma característica de um excelente isolante mostrando-se adequado para a fabricação de dispositivos moleculares do tipo elétrico e óptico. Os dispositivos moleculares ópticos e elétricos foram obtidos pela técnica de \"spin coating\" a partir de soluções contendo o polímero de PS e as moléculas de Alq3 e Rh590 em solvente orgânico, mostrando que esta técnica permite a obtenção de filmes com espessura de 200nm e rugosidade com RMS da ordem de 2nm. Foi verificado que filmes de PS contendo moléculas de Alq3 e Rh590 podem ser utilizadas como dispositivos de transferência de energia e que a eficiência de transferência depende da sobreposição da banda de emissão do Alq3, banda de absorção da Rh590 e a concentração relativa das moléculas; tendo sido obtido dispositivos com ate 86 % de eficiência de transferência. Foi verificado que os dispositivos de ITO/PS:Alq3/Al e ITO/PS:Alq3:Rh590/Al apresentam mecanismos de transporte do tipo de transporte limitado por cargas armadilhadas nos níveis de defeito situadas na região da banda proibida entre o HOMO e LUMO das moléculas de Alq3 e Rh590. Os dispositivos elétricos de ITO/PS:Alq3/Al mostraram a existência de efeito memória que foram atribuídos a mudanças nos estados de ocupação de níveis altamente localizados (armadilhas) e à existência de nano- partículas metálicas no interior do filme de PS:Alq3 promovendo a transferência de elétrons por efeitos de tunelamento ressonante. Os resultados obtidos no presente trabalho em relação aos mecanismos de transferência de energia e eletrônica apresentam-se promissores para futuras aplicações em dispositivos moleculares como memórias moleculares, chaves moleculares, dispositivos de emissão (OLEDs). / The aim of the present work was to study and analyses the energy and electron transfer process in molecular devices. The molecular devices were fabricated by using the polystyrene polymer because this material, as it was verified in this work, showed a good insulator features. The optical and electrical molecular devices were fabricated by using the spin-coating techniques from the PS, Alq3 and Rh520 solution in organic solvent. The thin film obtained by this technique showed a 200 nm of thickness and 2 nm RMS of roughness, that it is a good parameter values in order to obtain a molecular devices. The thin film of PS with Alq3 and Rh520 as host molecules acts as a good energy transfer device yielding the transfer efficiency of 86%. The transfer efficiency showed dependence on relative concentration of molecules in the PS film and in the good emission an absorption spectra overlapping of molecules. The molecular device of type ITO/PS:Alq3/Al and ITO/PS:Alq3:Rh520/Al used as molecular device of electrical type showed that the electrons transfer mechanism is limited by charge trapped in the localized level between HOMO and LUMO levels of the molecules. The devices of the type ITO/PS:Alq3/Al showed additionally a memory and negative resistance features that it was attributed to the change in the charge trapped levels due to device polarization and to the existence of Al nano particles into the PS film. The results obtained in this work showed high cientific and technological relevance in order to project and fabricate the molecular devices.

For direct cycle gas cooled high temperature reactor designs, operating conditions may be limited as a result of excessive maintenance dose rates caused by the 110mAg source term on the turbine. The accurate prediction of silver fission and activation products’ release during normal operation is required to ensure regulatory compliance and economic viability of planned power plants. Fuel qualification programs should provide satisfactory results to ensure correct analyses, but will however not be available for many years. In the meantime data from the German fuel development program may be utilized. Traditionally diffusion models were used to derive transport parameters from limited irradiation testing of fuel materials and components. Best estimates for all applicable German fuel irradiation tests with defendable uncertainty ranges were never derived. However, diffusion theory and current parameters cannot account for all irradiation and heat-up test results, and for some tests, it appears unacceptably conservative. Other transport mechanisms have been suggested and alternative calculation models are being considered. In this thesis the relevant German material and irradiation tests were evaluated with the current PBMR metallic fission product release calculation model. Transport through all the fuel materials and components and from the sphere to the coolant gas was considered and best possible models and parameters were suggested. For the transport of silver through the SiC layer an alternative suggested model called the Molecular Vapour Transport Release (MVR) Model was evaluated against the traditional diffusion model. From this evaluation it was shown that classical diffusion modelling was still a viable model to predict silver transport in SiC. The MVR model was found to be a feasible model as well. However, due to the much larger verification and validation effort required, it was decided to use the diffusion model until such time that experimental results become available that might elucidate the exact physical transport model. The evaluation also showed that the diffusion model used must be quantified in a detailed evaluation of all applicable irradiation tests. A study of all German irradiation tests was previously performed and the applicable irradiation tests were identified. A detailed evaluation of these irradiation tests were performed with an updated diffusion model. New transport and material parameters were derived in this detailed evaluation and compared with existing values. An evaluation of some heat-up tests of irradiated fuel spheres was performed to assess the range for which the newly derived transport parameters are valid. The different models with their old and newly derived parameters were used to analyse sample PBMR cores. Recommendations were made to the suitability of the different models and parameters for future PBMR silver fission and activation product analyses. / Thesis (DPhil)--University of Pretoria, 2009. / Physics / unrestricted