Understanding the hydrological controls on subsurface flow and transport is of considerable importance in the study of reclaimed landscapes in the oil sands region of Canada. A significant portion of the reclaimed landscape will be comprised of a thin veneer (~ 1 m) of clay-rich reclamation soil overlying saline-sodic shale overburden, which is a waste by-product from the mining process. The global objective of this study was to investigate the first-order controls on soil moisture and salt transport dynamics within clay-rich reclamation covers overlying low permeability waste substrates. The study site is located in a cold, semi-arid climate in the oil sands region of northern Alberta. Preferential flow was the dominant mechanism responsible for the development of perched water table conditions on the cover-waste interface during the spring snow melt. Hydrological and geochemical data indicated that snowmelt infiltration occurs via the macroporosity while the ground is still frozen. An isotope hydrograph separation conducted on water collected in a weeping tile confirmed the presence of fresh snowmelt water at the onset of subsurface flow. This water transitions to a chemical signature that is comprised of approximately 80% connate pore water as a result of chemical equilibration between pore water in the soil matrix and fresh water in the macropores.<p>Detailed mapping of the spatial distribution of soil moisture and salts within a reclamation cover indicated the lower-slope positions are wetter due to the accumulation surface run-off and frozen ground infiltration in spring. Increased soil moisture conditions in lower-slope positions accelerate salt ingress, while drier conditions in middle and upper-slope positions attenuate salt ingress. The data indicated that fresh snowmelt water is bypassing the soil matrix higher in the cover profile. Subsurface flow and deep percolation are key mechanisms mitigating vertical salt ingress in lower and upper slope positions. The mesotopography of the cover-waste interface imposes a direct control on the depth of perched water and the downslope routing of water. Undulations in the cover-waste interface cause the depth of perched water to vary considerably (± 20 60 cm) over short distances (< 5 m), while saturated subsurface flow is routed through the lowest elevations in the cover profile. A numerical analysis of subsurface flow was able to simulate both the discharge rate and cumulative volume of flow to a weeping tile. Composite hydraulic functions were used in the simulations to account for the increased hydraulic conductivity and drainable porosity created by the macroporosity at near-saturated conditions. The transient Na+ concentration of discharge water was modelled using the concept of an equivalent porous medium. The good match between measured and modelled data verified the conceptual model, which contends that saturated subsurface flow is dominated by the fracture network and that the concentration of discharge water is function of the depth of perched water. Finally, the results from this study suggest the mesotopography of the cover-waste interface could be used to manage excess water and salts within the landscape.

Understanding the hydrological controls on subsurface flow and transport is of considerable importance in the study of reclaimed landscapes in the oil sands region of Canada. A significant portion of the reclaimed landscape will be comprised of a thin veneer (~ 1 m) of clay-rich reclamation soil overlying saline-sodic shale overburden, which is a waste by-product from the mining process. The global objective of this study was to investigate the first-order controls on soil moisture and salt transport dynamics within clay-rich reclamation covers overlying low permeability waste substrates. The study site is located in a cold, semi-arid climate in the oil sands region of northern Alberta. Preferential flow was the dominant mechanism responsible for the development of perched water table conditions on the cover-waste interface during the spring snow melt. Hydrological and geochemical data indicated that snowmelt infiltration occurs via the macroporosity while the ground is still frozen. An isotope hydrograph separation conducted on water collected in a weeping tile confirmed the presence of fresh snowmelt water at the onset of subsurface flow. This water transitions to a chemical signature that is comprised of approximately 80% connate pore water as a result of chemical equilibration between pore water in the soil matrix and fresh water in the macropores.<p>Detailed mapping of the spatial distribution of soil moisture and salts within a reclamation cover indicated the lower-slope positions are wetter due to the accumulation surface run-off and frozen ground infiltration in spring. Increased soil moisture conditions in lower-slope positions accelerate salt ingress, while drier conditions in middle and upper-slope positions attenuate salt ingress. The data indicated that fresh snowmelt water is bypassing the soil matrix higher in the cover profile. Subsurface flow and deep percolation are key mechanisms mitigating vertical salt ingress in lower and upper slope positions. The mesotopography of the cover-waste interface imposes a direct control on the depth of perched water and the downslope routing of water. Undulations in the cover-waste interface cause the depth of perched water to vary considerably (± 20 60 cm) over short distances (< 5 m), while saturated subsurface flow is routed through the lowest elevations in the cover profile. A numerical analysis of subsurface flow was able to simulate both the discharge rate and cumulative volume of flow to a weeping tile. Composite hydraulic functions were used in the simulations to account for the increased hydraulic conductivity and drainable porosity created by the macroporosity at near-saturated conditions. The transient Na+ concentration of discharge water was modelled using the concept of an equivalent porous medium. The good match between measured and modelled data verified the conceptual model, which contends that saturated subsurface flow is dominated by the fracture network and that the concentration of discharge water is function of the depth of perched water. Finally, the results from this study suggest the mesotopography of the cover-waste interface could be used to manage excess water and salts within the landscape.

Providing sustainable supplies of water and energy is a critical global challenge. Polymer membranes dominate desalination and could be crucial to power generation applications, which include reverse osmosis (RO), nanofiltration (NF), forward osmosis (FO), pressure-retarded osmosis (PRO), electrodialysis (ED), membrane capacitive deionization (CDI), and reverse electrodialysis (RED). Improved membranes with tailored water and salt transport properties are required to extend and optimize these technologies. Water and salt transport structure/property relationships provide the fundamental framework for optimizing polymer materials for membrane applications. The water and salt transport and free volume properties of a series of sulfonated styrenic pentablock copolymers were characterized. The polymers' water uptake and water permeability increase with degree of sulfonation, and the block molecular weights could be used to tune water uptake, permeability, and selectivity properties. The presence of fixed charge groups, i.e., sulfonate groups, on the polymer backbone influence the material's salt transport properties. Specifically, the salt permeability increases strongly with increasing salt concentration, and this increase is a result of increases in both salt sorption and diffusivity with salt concentration. The data for the sulfonated polymers, including a sulfonated polysulfone random copolymer, are compared to those for an uncharged polymer to determine the influence of polymer charge on salt transport properties. The sulfonated styrenic pentablock copolymer permeability data are compared to literature data using the water permeability and water/salt selectivity tradeoff relationship. Fundamental transport property comparisons can be made using this relationship. The effect of osmotic de-swelling on the polymers and the transport properties of composite membranes made from sulfonated styrenic pentablock copolymers are also discussed. The sulfonated styrenic pentablock copolymers were exposed to multi-valent ions to determine their effect on the polymer's salt transport properties. Magnesium chloride permeability depends less on upstream salt concentration than sodium chloride permeability, presumably due to stronger association between the sulfonate groups and magnesium compared to sodium ions. Triethylaluminum was used to neutralize the polymer's sulfonic acid functionality and presumably cross-link the polymer. The mechanical, transport, and free volume properties of these aluminum neutralized polymers were studied. / text

Este trabalho tem como objetivos estudar a variabilidade das propriedades hidrográficas e da circulação durante ciclos completos de maré, classificar o sistema estuarino com o diagrama estratificação-circulação de Hansen & Rattray, calcular o transporte resultante de sal e a contribuição relativa dos termos advectivos, de difusão turbulenta e a parcela dispersiva, e estudar a influência das alterações ocorridas na descarga fluvial. Medidas de temperatura, salinidade e correntes foram realizadas no verão, outono, inverno e primavera, durante marés de sizígia e quadratura. Os perfis hidrográficos foram executados em intervalos horários durante ciclos completos de maré (13 horas), em três estações fixas (Barra de Cananéia, Baía do Trapandé e sul do Mar de Cananéia). A descarga fluvial média foi estimada através de dados climatológicos históricos da região. Os resultados sugerem mudanças no comportamento hidrodinâmico do sistema após a abertura do canal Valo Grande, com intensificação das correntes e aumento na estratificação vertical da salinidade. O aporte fluvial foi mais intenso (uma ordem de grandeza) que o obtido antes do rompimento da barragem do Valo Grande. As defasagens encontradas entre oscilações e correntes de maré, nas três estações fixas, indicam que a onda de maré se propaga pelo sistema como onda mista. A estação da Barra de Cananéia apresentou os maiores valores médios de salinidade e correntes mais intensas, sendo o oposto para a Baía do Trapandé, sugerindo que as trocas entre as águas oriundas da drenagem continental e da região costeira adjacente são mais efetivas pelo canal do Mar de Cananéia. O transporte de sal foi dominado principalmente pela parcela gerada pela descarga fluvial, seguida (com uma ordem de grandeza menor) pelas parcelas geradas pelo deslocamento da onda de maré (marés de sizígia) ou pela circulação gravitacional (marés de quadratura). As demais parcelas apresentam valores máximos inferiores a duas ordens de grandeza em relação à parcela dominante. A classificação do sistema estuarino-lagunar apresentou variações nas escalas de tempo quinzenal e sazonal, sendo sistema classificado como Tipo 2b no verão e Tipo 2a no inverno, ambos em maré de sizígia. No outono e primavera, o sistema foi classificado como Tipo 2b em marés de sizígia e Tipo 2a em marés de quadratura. / The aim of this work is to examine variations of physical water properties and estuarine circulation during complete tide cycle, to classify the estuary through Hansen and Rattray stratification-circulation diagram, to calculate salt transport and relative contribution of advection process, turbulent diffusion and dispersion, and to study the influences of alterations in fresh water discharge. Temperature, salinity and currents sampling were made in summer, autumn, winter and spring during neap and spring tides. Hydrographic profile measurements were accomplished in three fixed stations (Cananéia Bar, Trapandé Bay and south of Cananéia Sea) in hourly intervals, during a complete tidal cycle (13 hours). The medium fresh water discharge was evaluated through semi-empiric equations based on data climatological reports. The obtained results may suggest hydrodynamic system changes after the opening of the Valo Grande channel with currents intensification and increase in the salinity vertical stratification. The fresh water discharge estimative showed an increase in one order of greatness, if compared to obtained data found in recent works done when Valo Grande channel was closed. The differences found in the oscillation and tide current, in the three studied stations, indicated that the tide wave spreads in the system as a mixed wave. The station of Cananéia Bar presented the largest medium values of salinity and the most intense currents, being the opposite for the Bay of Trapandé, suggesting that the changes among the waters originating from continental drainage and adjacent coastal area are more effective for the Cananéia Sea. The transport of salt was dominated mainly by river discharge, with approximately an order of smaller greatness, followed by portions generated by tide wave displacement (in spring tides) or for the portion generated by the circulation gravitacional (in neap tides). The other portions presented inferior maximum values in two orders of greatness in relation to the dominant portion. The classification of the estuary-lagoon system showed variations in the scales of biweekly and seasonal time, being three fixed stations classified as Type 2b estuary in the summer and Type 2a estuary in the winter. In autumn and spring, during spring tides, the system changes to a Type 2b estuary, and during neap tides to a Type 2a estuary.

Este trabalho tem como objetivos estudar a variabilidade das propriedades hidrográficas e da circulação durante ciclos completos de maré, classificar o sistema estuarino com o diagrama estratificação-circulação de Hansen & Rattray, calcular o transporte resultante de sal e a contribuição relativa dos termos advectivos, de difusão turbulenta e a parcela dispersiva, e estudar a influência das alterações ocorridas na descarga fluvial. Medidas de temperatura, salinidade e correntes foram realizadas no verão, outono, inverno e primavera, durante marés de sizígia e quadratura. Os perfis hidrográficos foram executados em intervalos horários durante ciclos completos de maré (13 horas), em três estações fixas (Barra de Cananéia, Baía do Trapandé e sul do Mar de Cananéia). A descarga fluvial média foi estimada através de dados climatológicos históricos da região. Os resultados sugerem mudanças no comportamento hidrodinâmico do sistema após a abertura do canal Valo Grande, com intensificação das correntes e aumento na estratificação vertical da salinidade. O aporte fluvial foi mais intenso (uma ordem de grandeza) que o obtido antes do rompimento da barragem do Valo Grande. As defasagens encontradas entre oscilações e correntes de maré, nas três estações fixas, indicam que a onda de maré se propaga pelo sistema como onda mista. A estação da Barra de Cananéia apresentou os maiores valores médios de salinidade e correntes mais intensas, sendo o oposto para a Baía do Trapandé, sugerindo que as trocas entre as águas oriundas da drenagem continental e da região costeira adjacente são mais efetivas pelo canal do Mar de Cananéia. O transporte de sal foi dominado principalmente pela parcela gerada pela descarga fluvial, seguida (com uma ordem de grandeza menor) pelas parcelas geradas pelo deslocamento da onda de maré (marés de sizígia) ou pela circulação gravitacional (marés de quadratura). As demais parcelas apresentam valores máximos inferiores a duas ordens de grandeza em relação à parcela dominante. A classificação do sistema estuarino-lagunar apresentou variações nas escalas de tempo quinzenal e sazonal, sendo sistema classificado como Tipo 2b no verão e Tipo 2a no inverno, ambos em maré de sizígia. No outono e primavera, o sistema foi classificado como Tipo 2b em marés de sizígia e Tipo 2a em marés de quadratura. / The aim of this work is to examine variations of physical water properties and estuarine circulation during complete tide cycle, to classify the estuary through Hansen and Rattray stratification-circulation diagram, to calculate salt transport and relative contribution of advection process, turbulent diffusion and dispersion, and to study the influences of alterations in fresh water discharge. Temperature, salinity and currents sampling were made in summer, autumn, winter and spring during neap and spring tides. Hydrographic profile measurements were accomplished in three fixed stations (Cananéia Bar, Trapandé Bay and south of Cananéia Sea) in hourly intervals, during a complete tidal cycle (13 hours). The medium fresh water discharge was evaluated through semi-empiric equations based on data climatological reports. The obtained results may suggest hydrodynamic system changes after the opening of the Valo Grande channel with currents intensification and increase in the salinity vertical stratification. The fresh water discharge estimative showed an increase in one order of greatness, if compared to obtained data found in recent works done when Valo Grande channel was closed. The differences found in the oscillation and tide current, in the three studied stations, indicated that the tide wave spreads in the system as a mixed wave. The station of Cananéia Bar presented the largest medium values of salinity and the most intense currents, being the opposite for the Bay of Trapandé, suggesting that the changes among the waters originating from continental drainage and adjacent coastal area are more effective for the Cananéia Sea. The transport of salt was dominated mainly by river discharge, with approximately an order of smaller greatness, followed by portions generated by tide wave displacement (in spring tides) or for the portion generated by the circulation gravitacional (in neap tides). The other portions presented inferior maximum values in two orders of greatness in relation to the dominant portion. The classification of the estuary-lagoon system showed variations in the scales of biweekly and seasonal time, being three fixed stations classified as Type 2b estuary in the summer and Type 2a estuary in the winter. In autumn and spring, during spring tides, the system changes to a Type 2b estuary, and during neap tides to a Type 2a estuary.