Flow and mean residence time in epikarst and unsaturated zone was studied above the Ochoz cave in the Moravian Karst. I studied various flow components with different residence time in unsaturated zone and the influence of soil and epikarst on seepage composition and residence time by means of several methods (longterm monitoring of conductivity, flowrate of seepage and soil water, use of environmental tracers - 18 O, 3 H, CFC and SF6, flow into the soil and detailed sampling during intesive rain events). Seepage sites Kašna in the Rudické propadání cave system and Mapa Republiky in Býčí skála were reference localities in unsaturated zone. For comparison I modeled residence time in saturated zone: at Kaprálka outlet close to the Ochoz cave, at Stará řeka (Rudické propadání) and Konstantní přítok (Amatérská cave). Mean residence time in unsaturated zone above the Ochoz cave reaches 7 - 20 years, while it is only few months in the soil (1 - 8 months, depending on the depth). At Kašna seepage site, the reasidence time is similar to the Ochoz cave - about 18 - 20 years, at Mapa republiky seepage site, it reaches 150s year due to unusual geological settings. Mean residence time in order of 10 - 20 years corresponds to storativity values (0.6 % in average) calculated from parallel water level recession...

O modelo numérico Delft3D-Flow foi utilizado nos estudos da distribuição e variabilidade de propriedades termohalinas, e da circulação tridimensional do sistema estuarino dos rios Caravelas e Peruípe-SERCP. Os resultados do modelo foram validados quantitativamente usando dados experimentais de marés de quadratura e de sizígia de correntes e salinidades em quatro estações fixas (duas em cada um dos estuários de Caravelas e Nova Viçosa). No processamento foram aplicadas inicialmente condições iniciais homogêneas da salinidade, densidade e dos coeficientes cinemáticos de viscosidade e difusividade vertical, e após quatro semanas de simulação foram extraídos resultados de diferentes condições. Esses resultados foram utilizados como condições iniciais mais realistas, tendo o campo espacial variado das propriedades termohalinas, e dos parâmetros físicos. Essas novas condições iniciais permitiram pular o tempo transiente otimizando assim as simulações subsequentes. A validação das simulações foi feita com base nas medições da campanha de verão, por causa do atraso do período chuvoso a vazão do rio Peruípe foi bem representativa para condições de inverno e, portanto, seria redundante usar as forçantes dos rios com valores tão próximos na validação, além da necessidade da demanda de um tempo muito maior nas analise comparativas dos resultados. Durante o verão (janeiro de 2008), os dados de vazão do rio Peruípe obtidos na Agência Nacional de Águas (ANA) levaram a estimativa da descarga fluvial de ~ 20 m3.s-1, com a extrapolação de ~ 4 m3.s-1 para vazão conjunta dos dois principais afluentes do canal estuarino do rio Caravelas (rios Cúpido e Jaburuna). As oscilações da maré foram simuladas satisfatoriamente para as quatro estações de controle utilizadas na validação, com valores médios do parâmetro Skill superiores a 0,97. As amplitudes da maré calculadas numericamente foram de aproximadamente 1,3 m e 2,5 m na quadratura e sizígia, respectivamente. Os resultados numéricos das simulações das velocidades foram melhores em condições de sizígia com valores médios do parâmetro Skill entre 0,77 e 0,93, enquanto que na quadratura esse parâmetro variou entre 0,38 a 0,65. Para a estrutura de salinidade durante as condições de maré de sizígia, melhores resultados no SERCP do skill e, portanto abrangendo as quatro estações de controle, foram confirmados pelos parâmetros Skill médios superiores a 0,83. Na maré de quadratura os correspondentes valores médios também foram relativamente altos, variando entre 0,73-0,85. Entretanto, houve dificuldades em simular adequadamente a alta estratificação (vertical e longitudinal) do estuário de Nova Vicosa, podendo-se atribuir esse fato à maior vazão do rio Peruípe, que é muito maior do que a do rio de Caravelas. Com os resultados da estrutura de salinidade a intrusão da massa de Água Tropical (AT) foi adequadamente representada nos quilômetros iniciais do canal estuarino do rio Caravelas, e na parte interna da desembocadura na região de Nova Viçosa. Movimentos bidirecionais foram observados nos resultados das simulações na preamar e baixamar, na região de desembocadura dos estuários da Caravelas e Nova Viçosa, movimentos estes forçados pela componente baroclínica da força de gradiente de pressão. Vale ressaltar que o efeito baroclínico ficou mais visível nos instantes da baixamar. Na preamar para a maior parte destas duas regiões verificou-se apenas um pequeno desvio no sentido das correntes entre superfície (Z = -0,1) e fundo (Z = -0,9) e em geral inferior a 30 graus. Usando os traçadores lagrangeanos virtuais lançados ao longo dos canais estuarinos das entradas norte (Caravelas) e sul (Nova Viçosa) do SERCP foi obtido como resultado um tempo de residência relativamente pequeno e comparável ao estuário tropical do rio Curimataú. No trecho analisado no canal estuarino do rio Caravelas, a ~ 3 km e ~ 12 km distantes da Boca do Tomba o tempo de residência médio foi ~ 4,2 dias e ~10,3 dias, respectivamente. Já no estuário de Nova Viçosa, ou canal estuarino do rio Peruípe, apenas o trecho inicial de 5 km foi considerado para o lançamento dos traçadores, e os tempos de residência de ~ 1,5 dias e 2,5 dias foram estimados para as posições de ~2,5 km e 5,0 km distantes da desembocadura. O modelo analítico proposto e usado no cálculo de tempo de residência teve resultados comparáveis aos obtidos pelas simulações pelo método lagrangeano do Delft-3D Flow. Diferentemente, o modelo LOICZ apresentou valores bem diferentes do tempo de residência para os seis estuários analisados (Caravelas, Nova Viçosa, Curimataú, Hudson, Conwy and Mersey), em geral bem inferiores aos do modelo proposto, indicando assim uma possível estimativa maior do fluxo difusivo na formulação do modelo LOICZ. / The numerical model Delft-Flow was used to study the spatial distribution and variability of the termohaline properties, and the tridimensional circulation in the estuarine system of the rivers Caravelas and Peruípe. The model results were validated quantitatively using field data of tidal oscilation and currents, and salinity measurements during neap and spring tides at four mooring stations, two in each estuary. In the data processing homogeneous conditions were used initially for the fields of salinity, density and the vertical kinematic coeficients of viscosity and diffusivity, then after four weeks of running simulation those fields were saved with spatially varied conditions. Those results were used for a more realistic initial condition, thus having a varied field of the termohaline properties, and of the physical parameters. The new initial conditions allowed avoiding the transient time and thus optimizing the following simulations. The model evaluation was done based on measurements undertaken during the summer season, because of the delay in the raining season, the Peruípe river discharge was low and more representative of dry season condition, for those reasons we just used the measurement taken in the January 2008. In the summer the measurements of the Peruíbe river discharge taken from the Agência Nacional de Águas (ANA), and the river flow of was estimated at ~ 20 m3.s-1, with the extrapolation of ~ 4 m3.s-1 for the unified flow from the rivers Cúpido and Jaburuna, with contribute to the flow in the Caravelas estuary. Tidal oscillation at neap and spring tides were well simulated for the 4 controling sites used to the validation, and with the mean skill values over 0.97. The tidal amplitudes were numerical calculated and nearly between 1.3 and 2.5 meters at neap and spring tides, respectively. The numerical results of the velocities were better simulated in spring tides with the mean skill values in the range of 0.77 and 0.93, while at neap tides this parameter varied between 0.38 and 0.65. For the salinity structure at spring tides good results in the estuarine system were achieved, hence comprising all the controling station for validation, with all mean skill values over 0.83. At neap tides the corresponding mean skill values were relatively high, varing in the range of 0.73-0.85. In addition, there were difficulties in simulation adequately the highly vertical and longitudinal stratification of the Nova Vicosa estuary. That was caused by the stronger river inflow of the Peruípe River, which is much higher than the inflow by Caravelas River. The intrusion of the Tropical Water mass (TW) was properly simulated given the right distribution of the salinity along the first quilometers of the estuarine channel of Caravelas, and the internal part of the Nova Viçosa estuarine mouth. Bidirectional movements were observed from the model outputs at the high and low tides, at the region near the mouth of both, Caravelas and Nova Viçosa estuary. Those moviments are forced by the baroclinic component of the pressure gradient. Is worth to mention the the baroclinic effect was better observed at the low tides of these regions. At high tide most of areas showed only a small change in the current direction between surface (Z = -0.1) and bottom (Z = -0.9) and usually smaller than 30 degrees. The virtual lagrangian drifters released along the estuarine channels of Caravelas (north) and Nova Viçosa (south) have shown a residence time relatively short, and comparable to the Curimataú tropical estuary. In the released location between 3 and 12 km of distance from the Caravelas mouth, the residence time was in the range of 4.2 and 10.3 days. Differently, at the Nova Viçosa estuary, only the first 5 km were studied and the residence time of 1.5 and 2.5 days was estimated for the respectives positions of 2.5 and 5.0 km away from the mouth. The analytical model proposed and used to calculate the residence time leaded to results comparable to the results from the numerical simulation using the Lagrangian method of the Delft-3D Flow. Differently, the LOICZ model has shown results really different of the residence time for all the six estuaries (Caravelas, Nova Viçosa, Curimataú, Hudson, Conwy and Mersey), and in general much smaller then the results from the proposed formula, thus indicating a possible overestimation of the diffusive flux assumed in the LOICZ formulation.

Os processos oxidativos avançados são promissores para a degradação de compostos orgânicos resistentes aos tratamentos convencionais, como o fenol. A fluidodinâmica computacional (CFD) tornou-se uma poderosa ferramenta para analisar processos fotoquímicos por resolver os balanços acoplados de quantidade de movimento, de massa e de radiação. O objetivo deste trabalho é investigar o processo UV/H2O2 num reator fotoquímico anular usando CFD e um modelo cinético mais realista. O modelo em CFD foi criado de forma progressiva. Inicialmente, foram determinados os campos de velocidade para três vazões (30, 60 e 100 L/h). Considerou-se dois diâmetros de lâmpada para reproduzir a configuração experimental do sistema. A discretização foi feita com malhas tetraédricas variando entre 390 000 e 1 200 000 elementos. Quatro modelos de turbulência RANS foram analisados: k-e, k-w, o shear stress transport (SST) e o modelo de tensões de Reynolds (RSM). O campo de velocidades foi validado comparando a DTR com seu levantamento experimental. A próxima etapa foi incluir o mecanismo de degradação de fenol proposto por Edalatmanesh, Dhib e Mehrvar (2008) no modelo em CFD. Trata-se de um modelo cinético baseado em equações dinâmicas para todas as espécies. O campo de radiação foi calculado pelo modelo radial e pela solução da equação de transporte de radiação através do método discrete transfer. As simulações reproduziram dados experimentais abrangendo uma larga gama de concentrações iniciais de fenol, razões molares H2O2/fenol e três potências de emissão das lâmpadas. O campo de velocidades obtido era dependente da vazão: o fluido pode manter movimento helicoidal sobre toda a extensão do reator ou se desenvolver como um escoamento pistonado. O modelo k-e não reproduziu bem o escoamento por não ser adequado para escoamentos rotativos. Os outros modelos geraram curvas de DTR com bom ajuste aos dados experimentais, especialmente o modelo k-w. O desvio médio entre as simulações de degradação de fenol e os dados experimentais é inferior a 8%. Verificou-se que, devido ao escoamento rotativo, os reagentes ficavam concentrados próximos à parede externa e migravam para a região da lâmpada ao longo do reator. A elevada intensidade de radiação na superfície da lâmpada criou uma camada ao seu redor na qual a fotólise do H2O2 ocorreu com grande taxa. Os radicais OH gerados nessa camada eram transportados para a região das paredes por convecção. Isso fez com que a maior parte do fenol fosse atacada na segunda metade do reator e gerou acúmulo do radical próximo à lâmpada na seção de saída do reator, já que o poluente já fora oxidado nessa área. O método discrete transfer previu intensidades de radiação maiores que o modelo radial, e, consequentemente, maior concentração de radicais OH. Os resultados satisfatórios indicam que CFD foi uma ferramenta adequada para analisar este escoamento reativo. / Advanced oxidation processes are a promising technology for degradation of organic compounds resistant to conventional treatments such as phenol. Computational fluid dynamics (CFD) has recently emerged as a powerful tool that allows a deeper understanding of photochemical processes in reactor engineering by solving the coupled momentum, mass and radiation balances. This work aimed to investigate the UV/H2O2 process in an annular photoreactor using CFD and a more realistic kinetic model. A progressive approach was used to develop the CFD reactor model. First, the velocity fields were determined for three volumetric flow rates (30, 60 and 100 L/h). Two lamp diameters were considered to reflect the experimental configuration of the system. Tetrahedral meshes varying form 390,000 to 1,200,000 elements were analyzed to achieve grid independence. For accounting turbulence effects, four RANS models were tested: k-e, k-w, the Shear Stress Transport (SST) and the Reynolds Stress models (RSM). The velocity field was validated through comparison to RTD experimental data. Next step was introducing the mechanism of phenol degradation proposed by Edalatmanesh, Dhib and Mehrvar (2008) into the CFD model. This kinetic model is based on dynamic equations for all species. The fluence rate field was calculated by the radial model and by solving the radiation transport equation with the discrete transfer method. Simulations reproduced experimental data spanning a wide range of initial phenol concentrations, H2O2/phenol molar ratios and three values for lamp power. It was found that the velocity field depends on the volumetric flow rate: either it maintains a swirling motion through the whole reactor or might develop like a plug flow. The k-e model did not represent the RTD data accurately, and the velocity field therefore, since it is not appropriate for swirling flows. The other turbulence models showed good match of RTD, especially the k-w model. Simulations of phenol degradation deviated less than 8% from experimental data. It was possible verified that, due to the swirling inlet effects, reactants got concentrated close to the outer wall and migrated on the lamp direction along the reactor path. High radiation intensities close to the lamp surface created a layer around it where photolysis of H2O2 took place with higher rates. OH radicals were generated in that layer and transported towards the outer wall by convection. This caused most of phenol to be consumed in the second half of the reactor and accumulation of the radical near the lamp and the reactor outlet, since the pollutant in this area was already oxidized. The discrete transfer method predicted higher incident radiation intensity than the radial model, and higher concentrations of OH radicals as a consequence. Satisfactory results indicated that CFD was an appropriate tool for analyzing this reactive flow.

A aplicação da técnica de leito de jorro na secagem de pastas têm sido objeto de inúmeras investigações nos últimos anos, devido a possibilidade de obtenção de produtos de alta qualidade em uma operação de reduzido custo. No presente trabalho, avaliou-se a influência dessa técnica sobre as características e o desempenho de liberação de microcápsulas contendo diferentes fármacos modelo. Microcápsulas de caseína-pectina contendo indometacina e paracetamol foram preparadas por coacervação e posteriormente secas por leito de jorro e por spray drying. Após a secagem por leito de jorro, verificou-se uma redução na quantidade de indometacina recuperada a partir das microcápsulas. Não se observou segregação do fármaco durante a operação de secagem por leito de jorro, indicando que a reduzida recuperação do mesmo foi resultado do estabelecimento uma interação fármaco-polímero, a qual ocorre especificamente entre a caseína e a indometacina. A avaliação físico-química desses materiais indicou que a interação proposta possui natureza covalente e os estudos in vivo de atividade antiinflamatória das microcápsulas contendo indometacina mostraram a irreversibilidade dessa ligação em ambiente biológico. A metodologia de estímulo resposta foi avaliada e otimizada para a determinação do tempo de residência das microcápsulas em leito de jorro. Apesar de confiáveis, os valores de tempo de residência obtidos não puderam ser correlacionados à formação da interação fármaco-polímero, por se apresentarem estáveis quando da variação das condições operacionais do secador. Por outro lado, a vazão e a temperatura do ar de secagem mostraram influência significante sobre a formação da referida interação. Posteriormente à investigação da interação indometacina-caseína, foi avaliada a funcionalidade das microcápsulas obtidas por leito de jorro e por spray drying. Para tanto, foram realizados estudos de liberação in vitro, os quais mostraram a similaridade entre os perfis de dissolução da indometacina do paracetamol independentemente do método de secagem empregado. Uma exceção está na formulação não reticulada contendo indometacina, que apresentou um elevado nível de ruptura após a secagem por leito de jorro. Os dados obtidos na avaliação da funcionalidade dos sistemas juntamente com a constatação experimental do maior aproveitamento energético na secagem por leito de jorro, permitem considerar que a utilização dessa técnica na secagem de microcápsulas é promissora, visto que a interação fármaco-polímero discutida nesse trabalho é específica e dependente do tipo de fármaco encapsulado / The use of spouted bed technique in the drying of paste has been subject to many researches in the past years due to the possibility of obtaining high quality products at low cost. In present work the influence of this technique on microcapsule drug delivery systems performance was evaluated. Casein-pectin microcapsules with entrapped indomethacin and acetaminophen were prepared using the complex coacervation method. Thereafter the coacervates were dried using the spouted bed and spray drying techniques. After spouted bed drying an interaction between indomethacin and casein was observed, with reduction of drug recovery from microcapsules. The mass balance studies showed the absence of indomethacin segregation during spouted bed drying, which indicates drug-polymer interaction. This interaction was not observed for acetaminophen. The physico-chemical evaluation suggests that the indomethacin interaction had covalent nature and in vivo studies showed its stability under enzymatic biological conditions. The microcapsule residence time during spouted bed drying was determined using a validated and optimized stimulus response method. Despite the reliable results obtained it was not possible to determine the influence of residence times on drug-polymer interaction due to the stability of those values with operational conditions. On the other hand air temperature and air flow rate during spouted bed drying affected significantly the degree of drug polymer interaction. In order to evaluate the spouted bed and spray dried microcapsule?s performance a dissolution study was performed. The results showed very similar drug release, with exception for the non-crosslinked formulations dried in spouted bed. These microcapsules were ruptured by spouted bed mechanical stresses. The results obtained on the microcapsules performance evaluation and the characteristics of thermal efficiency and high evaporative capacity of spouted bed demonstrate the potential application of casein-pectin spouted bed drying

A crescente demanda por biocombustíveis e a concorrência dos combustíveis fósseis torna necessária a otimização dos meios já existentes e o desenvolvimento de novas tecnologias para produção de biocombustíveis, principalmente em projetos envolvendo biorreatores e fotobiorreatores (FBR) industriais. A dinâmica dos fluidos computacional (CFD) vem sendo utilizada em vários trabalhos para o estudo de parâmetros fluidodinâmicos que podem influenciar no rendimento dos processos químicos envolvidos, como tensão de cisalhamento, perfis de velocidade, tempo de residência e a influência da geometria sobre esses parâmetros. Contudo, não existe ainda um número abrangente de trabalhos que utilize técnicas de otimização acopladas com a resolução numérica do problema fluidodinâmico. Em alguns estudos, algoritmos de otimização são utilizados para determinar os melhores coeficientes das reações químicas. No entanto, não há estudos, até o momento, que reportem a otimização multiobjetivo simultânea dos parâmetros geométricos e do escoamento aplicados a equipamentos da indústria sucro-energética. Neste contexto, o presente trabalho de pesquisa tem como objetivo contribuir para o avanço científico e tecnológico através da implementação de um software aberto (PyCFD-O) que permita o acoplamento CFD-otimização e o desenvolvimento das bases de uma metodologia de projeto otimizado bem como de operação de biorreatores e FBRs de escala industrial. O PyCFD-O foi testado em dois estudos de caso que podem ser estendidos a um fermentador contínuo e um FBR. Os parâmetros geométricos de ambos os reatores foram otimizados de forma a minimizar simultaneamente a tensão de cisalhamento e a variância da distribuição do tempo de residência. O software PyCFD-O mostrou-se robusto, revelando que o processo global de otimização realiza de fato a busca pela fronteira de Pareto. Além da obtenção das geometrias otimizadas, também foram discutidos a influência dos parâmetros geométricos na hidrodinâmica do escoamento em ambos os casos. / The growing demand for biofuels and its competition with fossil fuels create the need to optimize the existing resources and development of new technologies for production of biofuels, particularly in projects involving industrial bioreactors and photobioreactors (PBR). Computational fluid dynamics (CFD) has been used in several studies for the study of fluid dynamics parameters that can influence the performance of the chemical process involved, such as shear stress, velocity profiles, residence time and the influence of these parameters on the reactor geometry. However, there are lacks of studies that utilize optimization techniques coupled with the numerical resolution of the fluid dynamic problem. The use of optimization algorithms has been reported in some cases, but there have not been reports on studies combining the optimization of flow parameters and multiobjective algorithms to choose ideal geometric parameters applied to the equipment of the sugar-energy industry. In this context, this research project aims to contribute to the advancement of scientific and technological knowledge trhough the implementation of open source software (PyCFD-O) for the CFD-optimization coupling and the development of the bases of a methodology for optimal design and operation of industrial scale bioreactors and PBR. The PyCFD-O software was tested in two case studies with characteristics that can be extended to a continuos fermenter and PBR. The geometric parameters of both reactors were simultaneously optimized in order to minimize the shear stress and the variance of residence time distribuition. The PyCFD-O software showed robustness, revealing that overall optimization process actually performs the search of Pareto frontier. In addition to the geometry optimization, the influence of the geometrical parameters of the hydrodynamic of the flow was discussed in both case studies.

Este estudo apresenta a modelagem fluidodinâmica de um reator solar utilizado para Processos Oxidativos Avançados (POA). Desenvolveu-se um modelo que considera a fluidodinâmica, o campo de radiação e cinética da reação de actinometria química (ferrioxalato), em regime transiente. Essa modelagem foi feita utilizando-se o código de fluidodinâmica computacional PHOENICS. Para análise dos resultados de simulações com o modelo, consideraram-se os dados experimentais de actinometria química para um trecho do reator, constituído de dois tubos (hairpin), e de distribuição de tempos de residência (DTR), para o reator completo, constituído de dez tubos. Os dados experimentais foram obtidos por RIBEIRO (2009). O resultado da análise da distribuição do tempo de residência do reator completo mostrou que o modelo baseado em escoamento laminar apresentou uma maior aderência aos dados experimentais de DTR. Como os experimentos de actinometria foram realizados em trecho com dois tubos do reator, construiu-se a geometria do hairpin que apresentou uma DTR mais aderente aos modelos teóricos. Outra simplificação foi necessária para a modelagem do campo de radiação de forma mais precisa, adaptando-se o hairpin para um tubo reto simples. A partir dos resultados de actinometria química foi possível estimar, pelo modelo, a taxa de fótons incidentes na parede do reator. / This study consists of the fluid dynamic modeling of a solar reactor used in Advanced Oxidation Processes (AOP). The model was developed by considering fluid dynamics, radiation field and the kinetics of the chemical actinometry reaction (ferrioxalate) in transient regime. This modeling was developed using computational fluid dynamics (CFD) in PHOENICS. Simulation results based on the model were analyzed by comparing them with a set of chemical actinometry experimental data obtained by RIBEIRO (2009). This considered a reactor section constituted by two pipes (hairpin), and the residence time distribution (RTD) of the complete reactor, composed of ten pipes. Residence time distribution results showed that the laminar flow model presented a better fitting to experimental data. Since the actinometry experiments were carried out in a reactor section with two pipes, a new geometry was designed, which resulted in a better fitting of RTD results with theoretical models. In order to obtain a more precise radiation field model, another simplification was necessary, which consisted of assuming a straight cylindrical pipe geometry. The use of the chemical actinometry and the radiation field model enabled the estimation of the incident photons rate at reactor wall.

O modelo numérico Delft3D-Flow foi utilizado nos estudos da distribuição e variabilidade de propriedades termohalinas, e da circulação tridimensional do sistema estuarino dos rios Caravelas e Peruípe-SERCP. Os resultados do modelo foram validados quantitativamente usando dados experimentais de marés de quadratura e de sizígia de correntes e salinidades em quatro estações fixas (duas em cada um dos estuários de Caravelas e Nova Viçosa). No processamento foram aplicadas inicialmente condições iniciais homogêneas da salinidade, densidade e dos coeficientes cinemáticos de viscosidade e difusividade vertical, e após quatro semanas de simulação foram extraídos resultados de diferentes condições. Esses resultados foram utilizados como condições iniciais mais realistas, tendo o campo espacial variado das propriedades termohalinas, e dos parâmetros físicos. Essas novas condições iniciais permitiram pular o tempo transiente otimizando assim as simulações subsequentes. A validação das simulações foi feita com base nas medições da campanha de verão, por causa do atraso do período chuvoso a vazão do rio Peruípe foi bem representativa para condições de inverno e, portanto, seria redundante usar as forçantes dos rios com valores tão próximos na validação, além da necessidade da demanda de um tempo muito maior nas analise comparativas dos resultados. Durante o verão (janeiro de 2008), os dados de vazão do rio Peruípe obtidos na Agência Nacional de Águas (ANA) levaram a estimativa da descarga fluvial de ~ 20 m3.s-1, com a extrapolação de ~ 4 m3.s-1 para vazão conjunta dos dois principais afluentes do canal estuarino do rio Caravelas (rios Cúpido e Jaburuna). As oscilações da maré foram simuladas satisfatoriamente para as quatro estações de controle utilizadas na validação, com valores médios do parâmetro Skill superiores a 0,97. As amplitudes da maré calculadas numericamente foram de aproximadamente 1,3 m e 2,5 m na quadratura e sizígia, respectivamente. Os resultados numéricos das simulações das velocidades foram melhores em condições de sizígia com valores médios do parâmetro Skill entre 0,77 e 0,93, enquanto que na quadratura esse parâmetro variou entre 0,38 a 0,65. Para a estrutura de salinidade durante as condições de maré de sizígia, melhores resultados no SERCP do skill e, portanto abrangendo as quatro estações de controle, foram confirmados pelos parâmetros Skill médios superiores a 0,83. Na maré de quadratura os correspondentes valores médios também foram relativamente altos, variando entre 0,73-0,85. Entretanto, houve dificuldades em simular adequadamente a alta estratificação (vertical e longitudinal) do estuário de Nova Vicosa, podendo-se atribuir esse fato à maior vazão do rio Peruípe, que é muito maior do que a do rio de Caravelas. Com os resultados da estrutura de salinidade a intrusão da massa de Água Tropical (AT) foi adequadamente representada nos quilômetros iniciais do canal estuarino do rio Caravelas, e na parte interna da desembocadura na região de Nova Viçosa. Movimentos bidirecionais foram observados nos resultados das simulações na preamar e baixamar, na região de desembocadura dos estuários da Caravelas e Nova Viçosa, movimentos estes forçados pela componente baroclínica da força de gradiente de pressão. Vale ressaltar que o efeito baroclínico ficou mais visível nos instantes da baixamar. Na preamar para a maior parte destas duas regiões verificou-se apenas um pequeno desvio no sentido das correntes entre superfície (Z = -0,1) e fundo (Z = -0,9) e em geral inferior a 30 graus. Usando os traçadores lagrangeanos virtuais lançados ao longo dos canais estuarinos das entradas norte (Caravelas) e sul (Nova Viçosa) do SERCP foi obtido como resultado um tempo de residência relativamente pequeno e comparável ao estuário tropical do rio Curimataú. No trecho analisado no canal estuarino do rio Caravelas, a ~ 3 km e ~ 12 km distantes da Boca do Tomba o tempo de residência médio foi ~ 4,2 dias e ~10,3 dias, respectivamente. Já no estuário de Nova Viçosa, ou canal estuarino do rio Peruípe, apenas o trecho inicial de 5 km foi considerado para o lançamento dos traçadores, e os tempos de residência de ~ 1,5 dias e 2,5 dias foram estimados para as posições de ~2,5 km e 5,0 km distantes da desembocadura. O modelo analítico proposto e usado no cálculo de tempo de residência teve resultados comparáveis aos obtidos pelas simulações pelo método lagrangeano do Delft-3D Flow. Diferentemente, o modelo LOICZ apresentou valores bem diferentes do tempo de residência para os seis estuários analisados (Caravelas, Nova Viçosa, Curimataú, Hudson, Conwy and Mersey), em geral bem inferiores aos do modelo proposto, indicando assim uma possível estimativa maior do fluxo difusivo na formulação do modelo LOICZ. / The numerical model Delft-Flow was used to study the spatial distribution and variability of the termohaline properties, and the tridimensional circulation in the estuarine system of the rivers Caravelas and Peruípe. The model results were validated quantitatively using field data of tidal oscilation and currents, and salinity measurements during neap and spring tides at four mooring stations, two in each estuary. In the data processing homogeneous conditions were used initially for the fields of salinity, density and the vertical kinematic coeficients of viscosity and diffusivity, then after four weeks of running simulation those fields were saved with spatially varied conditions. Those results were used for a more realistic initial condition, thus having a varied field of the termohaline properties, and of the physical parameters. The new initial conditions allowed avoiding the transient time and thus optimizing the following simulations. The model evaluation was done based on measurements undertaken during the summer season, because of the delay in the raining season, the Peruípe river discharge was low and more representative of dry season condition, for those reasons we just used the measurement taken in the January 2008. In the summer the measurements of the Peruíbe river discharge taken from the Agência Nacional de Águas (ANA), and the river flow of was estimated at ~ 20 m3.s-1, with the extrapolation of ~ 4 m3.s-1 for the unified flow from the rivers Cúpido and Jaburuna, with contribute to the flow in the Caravelas estuary. Tidal oscillation at neap and spring tides were well simulated for the 4 controling sites used to the validation, and with the mean skill values over 0.97. The tidal amplitudes were numerical calculated and nearly between 1.3 and 2.5 meters at neap and spring tides, respectively. The numerical results of the velocities were better simulated in spring tides with the mean skill values in the range of 0.77 and 0.93, while at neap tides this parameter varied between 0.38 and 0.65. For the salinity structure at spring tides good results in the estuarine system were achieved, hence comprising all the controling station for validation, with all mean skill values over 0.83. At neap tides the corresponding mean skill values were relatively high, varing in the range of 0.73-0.85. In addition, there were difficulties in simulation adequately the highly vertical and longitudinal stratification of the Nova Vicosa estuary. That was caused by the stronger river inflow of the Peruípe River, which is much higher than the inflow by Caravelas River. The intrusion of the Tropical Water mass (TW) was properly simulated given the right distribution of the salinity along the first quilometers of the estuarine channel of Caravelas, and the internal part of the Nova Viçosa estuarine mouth. Bidirectional movements were observed from the model outputs at the high and low tides, at the region near the mouth of both, Caravelas and Nova Viçosa estuary. Those moviments are forced by the baroclinic component of the pressure gradient. Is worth to mention the the baroclinic effect was better observed at the low tides of these regions. At high tide most of areas showed only a small change in the current direction between surface (Z = -0.1) and bottom (Z = -0.9) and usually smaller than 30 degrees. The virtual lagrangian drifters released along the estuarine channels of Caravelas (north) and Nova Viçosa (south) have shown a residence time relatively short, and comparable to the Curimataú tropical estuary. In the released location between 3 and 12 km of distance from the Caravelas mouth, the residence time was in the range of 4.2 and 10.3 days. Differently, at the Nova Viçosa estuary, only the first 5 km were studied and the residence time of 1.5 and 2.5 days was estimated for the respectives positions of 2.5 and 5.0 km away from the mouth. The analytical model proposed and used to calculate the residence time leaded to results comparable to the results from the numerical simulation using the Lagrangian method of the Delft-3D Flow. Differently, the LOICZ model has shown results really different of the residence time for all the six estuaries (Caravelas, Nova Viçosa, Curimataú, Hudson, Conwy and Mersey), and in general much smaller then the results from the proposed formula, thus indicating a possible overestimation of the diffusive flux assumed in the LOICZ formulation.

The naturalisation and subsequent spread of non-indigenous plant species (NIPS) is a major problem for most regions of the world. Managing plant invasions requires greater understanding of factors that determine initial naturalisation and distribution of wild NIPS. By the year 2000, 2252 NIPS were recorded as wild (1773 fully naturalised and 479 casual) in New Zealand. From published literature and electronic herbaria records, I recorded year of discovery of wild populations, and regional distribution of these wild NIPS. I also recorded species related attributes hypothesised to affect naturalisation and/or distribution, including global trade, human activities, native range and biological data; and regional attributes hypothesised to affect distribution, including human population densities, land use/cover, and environmental data. I used interval-censored time-to-event analyses to estimate year of naturalisation from discovery records, then analysed the importance of historical, human activity, biogeographical and biological attributes in determining patterns of naturalisation. Typically, NIPS that naturalised earlier were herbaceous, utilitarian species that were also accidentally introduced and/or distributed, with a wide native range that included Eurasia, naturalised elsewhere, with a native congener in New Zealand. In the year 2000, 28% of wild NIPS occupied only one region, 18% occupied two regions, decreasing incrementally to 2.5 % for nine regions, but with 13.5% occupying all ten regions. I used generalised linear models (GLMs) with binomial distribution to determine predictors of whether a wild NIPS occupied ten regions or not, and GLMs with Poisson distribution for wild NIPS occupying 0 – 9 regions. As expected, the dominant effect was that species discovered earlier occupied more regions. Utilitarian wild NIPS that were also accidentally introduced and/or distributed, and wild NIPS with a native congener tended to be more widely distributed, but results for other attributes varied between datasets. Although numbers of wild NIPS recorded in regions of New Zealand were sometimes similar, composition of wild NIPS was often very different. I used nonmetric multidimensional scaling (NMDS) to determine dissimilarity in composition between regions. Then, after reducing correlation between predictor variables using principal components analyses (PCAs), I tested the importance of regional variables in determining the regional composition of wild NIPS using metaMDS. The density of human populations best explained the dissimilarity in composition, but temperature gradients and water availability gradients were also important. In the year 2000 more than 1100 (60%) of the 1773 fully naturalised NIPS in mainland New Zealand had each been recorded in Northland/Auckland and Canterbury, and at the other end of the scale, Southland and Westland each had fewer than 500 (30%). I used GLMs to analyse the importance of people and environment in determining the numbers of wild NIPS in each region. Because I conducted multiple tests on the same dataset I used sequential Bonferroni procedures to adjust the critical P-value. Only human population density was important in explaining the numbers of NIPS in the regions. Overall, humans were the dominant drivers in determining the patterns of naturalisation and spread, although environment helps determine the composition of NIPS in regions. Incorporating human associated factors into studies of wild NIPS helps improve the understanding of the stages in the naturalisation and spread process.

<p>The work in this thesis deals with (1) the effects of woody debris on stream channel morphology and retention of organic material, and (2) the dynamics of woody debris and its relation to riparian forest history and composition. The studied stream reaches are situated in mature, productive forests in the boreal zone of Sweden.</p><p>Wood variables were important predictors of the frequency of debris dams, pool area, the proportion of pools formed by wood, and variation in the bankfull channel width. Pools formed by woody debris were mainly created by damming and had larger surface areas and residual depths than pools formed by other agents. Stream reaches intersecting old-growth forest (with minor influence of forest management) had coarser and longer woody debris pieces, greater amounts of wood, more debris dams, and wood-formed pools compared to streams surrounded by forests influenced by selective logging.</p><p>The influence of past forest management on the quality and quantity of woody debris in streams were analyzed by using dendrochrnological methods. Selective loggings and absence of forest fires after 1831 resulted in lower input rates and a gradual replacement of pine by sruce over time. Residence times in stream channels of woody debris (>10 cm in basal diameter) were long and the oldest dated pieces of pine and spruce were over 300 and 100 years, respectively.</p><p>Dynamics of woody debris were explored by comparing wood volumes and characteristics between stream channels and their riparianforests and between old growth and managed sites. Wood volumes recorded in the stream channels exceeded, but were related to, the volumes found in the riparian forests. Limited input of woody debris by bank cutting and absence of slope processes suggest that recruitment processes of woody debri to stream channels are similar as in riparian forests and slow decay in channels results in greater volumes.</p><p>The retentiveness of organic material in stream channels was examined by using release and capture experiments in multiple reaces during varying discharges using different sizes of leaf mimics. Sixty eight percent of the variation in retention was explained by a multiple regression model including discharge and leaf mimic siz. Between 44 and 80% of the variation in retention among reaches was explained by channel constraint, gravel coverage, and woody debris variables as the most important. Estimates from a partial least squares (PLS) model suggest an increase in mean transport distances by 22 to 53% in managed forest streams compared to old growth conditions and in a low wood scenario, mean transport distances increased by 38 to 99% with larger increases for higher discharges and larger particle sizes.</p><p>To regain more pristine conditions of stream channels, management and restoration are needed to increase the amount of woody debris that recreates lost channel structures and increaes the retention of organic material.</p>

The feedbacks between hydrology and biogeochemical cycling of nitrogen (N) are of critical importance to global bioavailable N budgets. Human activities are dramatically increasing the amount of bioavailable N in the biosphere, which is causing increasingly frequent and severe impacts on ecosystems and human welfare. Streams are important features in the landscape for N cycling, because they integrate many sources of terrestrially derived N and control export to downgradient systems via internal source and sink processes. N transformations in stream ecosystems are typically very complex due to spatiotemporal variability in the factors controlling N biogeochemistry. Thus, it is difficult to predict if a particular stream system will function as a net source or sink of bioavailable N. A key location for N transformations in stream ecosystems is the hyporheic zone, where stream and ground waters mix. The hyporheic zone can be a source of bioavailable N via nitrification or a sink via denitrification. These N transformations are regulated by the physical and biogeochemical conditions of hyporheic zones. Natural heterogeneity in streams leads to unique combinations of both the physical and biogeochemical conditions which in turn result in unique N source and sink conditions. This dissertation investigates the relationships between physical and biogeochemical controls and the resulting fate of bioavailable N in hyporheic zones. The key physical factor investigated is the supply rate of solutes which is a function of transport processes - advection and dispersion, and transport conditions - hydraulic conductivity and flowpath length. Different physical conditions result in different characteristic residence times of water and solutes in hyporheic zones. The key biogeochemical factors investigated are the dynamics of oxygen (O₂), labile dissolved organic carbon (DOC), and inorganic bioavailable N (NH₄⁺ and NO₃⁻). This dissertation uses ¹⁵N isotope experiments, numerical modeling of coupled transport of the bioavailable N species, O₂ and DOC, and a suite of geophysical measurements to identify the key linkages between hydrological and biogeochemical controls on N transformations in hyporheic zones. Specifically, it was determined that the conditions governing the fate of hyporheic N are both the physical transport and reaction kinetics – the residence time of water and the O2 uptake rate. An important scaling relationship is developed by relating the characteristic timescales of residence time and O₂ uptake. The resulting dimensionless relationship, the Damköhler number for O₂, is useful for scaling different streams hyporheic zones and their role on stream N source – sink dynamics. More generally, these investigations demonstrate that careful consideration and quantification of hydrological processes can greatly inform the investigation of aquatic biogeochemical dynamics and lead to the development of process-based knowledge. In turn, this process-based knowledge will facilitate more robust approaches to quantifying and predicting biogeochemical cycles and budgets. / Graduation date: 2012 / Access restricted to the OSU Community at author's request from Sept. 21, 2011 - March 21, 2012