Nutrient enrichment, which can be detrimental to the health of aquatic systems, is one of the leading causes of impairment of our Nations? waters. Development and initial calibration of a hydrologic, hydrodynamic, and water quality model of dissolved oxygen and nutrient concentration for the St. Louis Bay watershed in coastal Mississippi is documented herein. The model was developed using the USEPA BASINS 3.0 analysis system and WinHSPF, a comprehensive watershed loading and transport modeling software. The resulting model simulates significant watershed and instream physical, chemical and biological processes including rainfall runoff and associated water quality from a variety of land use categories. Extensive data describing the study area, land use practices, hydrology and water quality are presented, analyzed and discussed relative to model development and adequacy to support future modeling projects. Integration of this data into a valuable water quality assessment model and preliminary model calibration is also presented.

No description available.

No description available.

No description available.

Freshwater reservoirs store, process, and emit to the atmosphere large quantities of carbon (C). Despite the important role of reservoirs in the global carbon cycle, it remains unknown how human activities are altering their carbon cycling. Climate change and land use are resulting in lower dissolved oxygen (DO) concentrations in freshwater ecosystems, yet more frequent, powerful storms are occurring that temporarily increase DO availability. The net effect of these opposing forces results in anoxia (DO < 0.5 mg L-1) punctuated by short-term increases in DO. The availability of DO controls alternate redox reactions in freshwaters, thereby determining the rate and end products of organic C mineralization, which include two greenhouse gases, carbon dioxide (CO2) and methane (CH4). I performed ecosystem-level DO manipulations and evaluated how changing DO conditions affected redox reactions and the production and emission of CO2 and CH4. I also explored how the magnitude and drivers of CH4 emissions changed spatio-temporarily in a eutrophic reservoir using time series models. Finally, I used a coupled data-modeling approach to forecast future emissions of CH4 from the same reservoir. I found that the depletion of DO results in the rapid onset of alternate redox reactions in freshwater reservoirs for organic C mineralization and greater production of CH4. When the anoxia occurred in the water column (vs. at the sediments), diffusive CO2 and CH4 efflux phenology was affected, and resulted in degassing occurring during storms before fall turnover. I observed that the magnitude of CH4 emissions varied along a longitudinal gradient of a small reservoir and that the environmental drivers of ebullition and diffusion can change substantially both over space (within one hundred meters) and time (within a few weeks). Finally, I developed a forecasting workflow that successfully predicted future CH4 ebullition rates during one summer season. My research provides insight to how changing DO conditions will alter redox reactions in the water column and greenhouse gas emissions, as well as provides a new technique for improving future predictions of CH4 emissions from freshwater reservoirs. Althogether, this work improves our understanding of how freshwater lake and reservoir carbon cycling will change in the future. / Doctor of Philosophy / Freshwater reservoirs store a lot of carbon in their sediments and emit a lot of carbon as greenhouse gases (carbon dioxide and methane) to the atmosphere. However, climate change, land use, and water quality management can change the chemical reactions that are responsible for the production of carbon dioxide and methane, which could have substantial effects on the global carbon budget. Here, I manipulated the oxygen conditions of a freshwater reservoir and monitored the chemistry and greenhouse gas emissions in the experimental reservoir relative to an upstream reference reservoir. I then estimated the methane emissions from the reservoir to understand how the chemistry and greenhouse gas emissions in freshwater reservoirs may change in the future. I found that reservoir oxygen availability controls the magnitude and timing of the chemical reactions that produce carbon dioxide and methane, which in turn alters greenhouse gas emissions. Additionally, I developed models that showed how the magnitude and drivers of methane emissions changed within a small reservoir over time. Finally, I was able to predict the timing and magnitude of methane bubbling from the sediments. Altogether, this work provides evidence how climate change, land use change, and water quality management will affect future water chemistry and greenhouse gas emissions from reservoirs.

Pecan Creek flows southeast through the City of Denton, Texas. Characterized as an urban watershed, the basin covers approximately 63.5 km2. Pecan Creek is an intermittent stream that receives nonpoint runoff from urban landuses, and the City of Denton's wastewater treatment plant, Pecan Creek Water Reclamation Plant, discharges effluent to the stream. Downstream from the City of Denton and the wastewater treatment plant, Pecan Creek flows about 6,000 m through agricultural, pasture, and forested landscapes into Copas Cove of Lake Lewisville, creating backwater conditions. Pecan Creek water quality and chemistry were monitored from August 1997 to October 2001. Water quality was influenced by seasonal, spatial, climatic, and diurnal dynamics. Wastewater effluent discharged from the Pecan Creek Water Reclamation Plant had the greatest influence on water quality of the stream and backwaters. Water quality monitoring of Pecan Creek demonstrated that dissolved oxygen standards for the protection of aquatic life were being achieved. Water quality modeling of Pecan Creek was completed to assess future increases in effluent flow from the Pecan Creek Water Reclamation Plant. Water quality modeling indicated that dissolved oxygen standards would not be achieved at the future effluent flow of 21 MGD and at NPDES permitted loadings. Model results with application of a safety factor indicated that the maximum allowable concentrations for a 21 MGD discharge would be 2.3 mg/L of ammonia and 7.0 mg/L of biochemical oxygen demand at summer conditions. Drought conditions that occurred from 1998 to 2001 reduced water levels in Lake Lewisville and impacted dissolved oxygen water quality in Pecan Creek. Water quality observations made during the period of drought allowed for the development of a model to estimate the zone of the dissolved oxygen sag in Pecan Creek based on reservoir elevation. Finally, monitoring results were analyzed with nonparametric statistical procedures to detect water quality changes in the backwater area of Pecan Creek, as influenced by storm events.

Este trabalho visou o desenvolvimento de sensores de oxigênio dissolvido (OD) utilizando tecnologias de filmes espessos, possibilitando baixo custo de produção, mantendo porém a durabilidade e precisão necessárias para o emprego no monitoramento de águas mananciais. Tal desenvolvimento também incluiu o desenvolvimento de circuitos eletrônicos próprios para o funcionamento completo e autônomo dos sensores. Aplicando-se o princípio de funcionamento do sensor eletroquímico de oxigênio dissolvido baseado na célula de Clark(1956), desenvolveu-se inicialmente esta célula confeccionada em PVC com dimensões tradicionais e, posteriormente, utilizou-se a tecnologia LTCC (Low Temperature Cofired Ceramics) como substrato do sensor em uma microconfiguração planar. Essa inovação permitiu estudar as facilidades de construção com este substrato, várias composições para o eletrólito, espessura das membranas em FEP e PDMS, e o uso das técnicas de medidas tais como polarização contínua, polarização pulsada e voltametria cíclica. Os sensores desenvolvidos foram estudados em condições de monitoramento contínuo e chegaram a alcançar 4 meses de durabilidade utilizando membrana de FEP com deriva de 0,14 % hora-1. Verificou-se através dos ensaios que a configuração da célula eletroquímica de 3 eletrodos estende a durabilidade dos microsensores, pois esta configuração atenua a redução da prata sobre o catodo. Devido a recente regulamentação da detecção óptica do OD pela ASTM, inclui-se neste trabalho o princípio da técnica de medição através da detecção da luminescência. Apresenta-se a implementação de um sistema óptico de detecção utilizando LEDs de alto brilho como fonte de excitação e fotodiodo com filtro de cor embutido para a detecção da intensidade luminescente de um complexo de rutênio (Ru(dpp)) imobilizado em filme sol-gel e em silicone PDMS. O sensor óptico imobilizado em filme sol-gel operando em modo contínuo apresentou a menor deriva (0,03 % hora-1) dentre os microssensores ópticos construídos. A adição de uma fina camada de silicone preto sobre a imobilização sol-gel proporcionou maior durabilidade e imunidade do filme à variação de salinidade da amostra sem prejudicar o tempo de resposta do sensor. / This work aims the development of a dissolved oxygen (DO) sensor using thick film technology, which has low cost of production and keeps sensors durability and precision acceptable for their use in the monitoring of water sources. This development also includes the complete electronic circuits for autonomous monitoring. Using the principles of oxygen electrochemical sensors based on Clark´s cell, this cell is initially built in PVC with traditional dimensions and aftwords build in LTCC (Low Temperature Co-fired Ceramics) technology as a substrate for the sensor in a microplanar configuration. This innovation allowed the study of constructive aspects, especially by changing substrate configuration, compositions for the electrolyte, thickness of the FEP or PDMS membrane, and the use of diverse electronic measurement techniques such as continuous polarization, pulsed polarization and cyclic voltammetry. Sensors submitted to continuous monitoring could reach 4 months of duration, using FEP membrane, drifting 0.14 % h-1. A 3 electrodes electrochemical cell configuration can extend the sensor´s life, presenting a low drift for both sensors types, because this new configuration attenuates the reduction of the silver over the cathode. Due to recent regulation of the optical detection of OD by ASTM, this work includes the measurement of DO through the detection of luminescent patterns. Such a system was developed by using high brightness LED´s as excitement sources and special photodiodes embedded with color filters as luminescence intensity detectors . The ruthenium complex (Ru(dpp)) immobilized in a sol-gel film and in PDMS was used as oxygen-sensitive material. The optical sensor immobilized in sol-gel film operating in continuous mode presented the lowest drift (0.03 % h-1) of all built sensors. The addition of a thin layer of black silicone over the sol-gel immobilization provided a greater durability and the immunity of the film and to sample salinity variation, without prejudice to the sensor response time.

Este trabalho visou o desenvolvimento de sensores de oxigênio dissolvido (OD) utilizando tecnologias de filmes espessos, possibilitando baixo custo de produção, mantendo porém a durabilidade e precisão necessárias para o emprego no monitoramento de águas mananciais. Tal desenvolvimento também incluiu o desenvolvimento de circuitos eletrônicos próprios para o funcionamento completo e autônomo dos sensores. Aplicando-se o princípio de funcionamento do sensor eletroquímico de oxigênio dissolvido baseado na célula de Clark(1956), desenvolveu-se inicialmente esta célula confeccionada em PVC com dimensões tradicionais e, posteriormente, utilizou-se a tecnologia LTCC (Low Temperature Cofired Ceramics) como substrato do sensor em uma microconfiguração planar. Essa inovação permitiu estudar as facilidades de construção com este substrato, várias composições para o eletrólito, espessura das membranas em FEP e PDMS, e o uso das técnicas de medidas tais como polarização contínua, polarização pulsada e voltametria cíclica. Os sensores desenvolvidos foram estudados em condições de monitoramento contínuo e chegaram a alcançar 4 meses de durabilidade utilizando membrana de FEP com deriva de 0,14 % hora-1. Verificou-se através dos ensaios que a configuração da célula eletroquímica de 3 eletrodos estende a durabilidade dos microsensores, pois esta configuração atenua a redução da prata sobre o catodo. Devido a recente regulamentação da detecção óptica do OD pela ASTM, inclui-se neste trabalho o princípio da técnica de medição através da detecção da luminescência. Apresenta-se a implementação de um sistema óptico de detecção utilizando LEDs de alto brilho como fonte de excitação e fotodiodo com filtro de cor embutido para a detecção da intensidade luminescente de um complexo de rutênio (Ru(dpp)) imobilizado em filme sol-gel e em silicone PDMS. O sensor óptico imobilizado em filme sol-gel operando em modo contínuo apresentou a menor deriva (0,03 % hora-1) dentre os microssensores ópticos construídos. A adição de uma fina camada de silicone preto sobre a imobilização sol-gel proporcionou maior durabilidade e imunidade do filme à variação de salinidade da amostra sem prejudicar o tempo de resposta do sensor. / This work aims the development of a dissolved oxygen (DO) sensor using thick film technology, which has low cost of production and keeps sensors durability and precision acceptable for their use in the monitoring of water sources. This development also includes the complete electronic circuits for autonomous monitoring. Using the principles of oxygen electrochemical sensors based on Clark´s cell, this cell is initially built in PVC with traditional dimensions and aftwords build in LTCC (Low Temperature Co-fired Ceramics) technology as a substrate for the sensor in a microplanar configuration. This innovation allowed the study of constructive aspects, especially by changing substrate configuration, compositions for the electrolyte, thickness of the FEP or PDMS membrane, and the use of diverse electronic measurement techniques such as continuous polarization, pulsed polarization and cyclic voltammetry. Sensors submitted to continuous monitoring could reach 4 months of duration, using FEP membrane, drifting 0.14 % h-1. A 3 electrodes electrochemical cell configuration can extend the sensor´s life, presenting a low drift for both sensors types, because this new configuration attenuates the reduction of the silver over the cathode. Due to recent regulation of the optical detection of OD by ASTM, this work includes the measurement of DO through the detection of luminescent patterns. Such a system was developed by using high brightness LED´s as excitement sources and special photodiodes embedded with color filters as luminescence intensity detectors . The ruthenium complex (Ru(dpp)) immobilized in a sol-gel film and in PDMS was used as oxygen-sensitive material. The optical sensor immobilized in sol-gel film operating in continuous mode presented the lowest drift (0.03 % h-1) of all built sensors. The addition of a thin layer of black silicone over the sol-gel immobilization provided a greater durability and the immunity of the film and to sample salinity variation, without prejudice to the sensor response time.

O Oceano Atlântico tem um papel importante na circulação global e nas influências oceânicas no sistema climático. Na sua porção sudoeste, a South Atlantic Meridional Overturning Circulation representa uma componente regional relevante para a circulação termohalina global. O monitoramento da presença e das características físicas (temperatura potencial, salinidade) das massas d\'água da região se faz necessário para avaliar a variabilidade da dinâmica da região. Neste contexto, da variabilidade, os parâmetros químicos (oxigênio dissolvido, fosfato, silicato e nitrato) tem grande importância, pois mesmo quando utilizados como traçadores complementares das massas d\'água, apresentam variações temporais e espaciais maiores que os parâmetros físicos devido aos processos biogeoquímicos. Em regiões costeiras, com todas as ressalvas, os nutrientes podem ser utilizados como traçadores complementares, como por exemplo, o silicato e fosfato foram considerados bom indicadores da Água de Plataforma do Prata (APP), e o nitrato, da Água Central do Atlântico Sul (ACAS). Na região fora da plataforma foram identificadas pelos parâmetros físicos e complementadas pelos parâmetros químicos as massas já citadas em literatura, Água Tropical (AT), ACAS, Água Intermediária Antártica (AIA) (máximo de oxigênio e nutrientes), Água Circumpolar Superior (ACS) e Água Circumpolar Inferior (ACI) (mínimo de oxigênio e máximo de nutrientes), Água Profunda do Atlântico Norte (APAN) (máximo de oxigênio e mínimo de nutrientes) e Água de Fundo Antártica (AFA) (máximo de silicato). Além disso, os nutrientes podem ser usados como ferramentas para estudar a dinâmica da região. Ao longo do transecto próximo a 34,5°S, foram observadas variações dos parâmetros físicos e químicos devido a processos de mistura podem indicar alterações na circulação das massas d\'água. O oxigênio dissolvido apresentou as maiores diferenças entre a porção leste e oeste na AT, AIA, ACS e APAN. O fosfato indicou o processo para a AT, ACS e APAN. O silicato apresentou variações mais evidentes para a AIA, ACS e APAN. E o nitrato apresentou uma distribuição mais homogênea, sem variações que permitam indicar alterações dos processos de circulação na região. / The Atlantic Ocean plays an important role in global circulation and in oceanic influences on the climate system. In its southwestern portion, the South Atlantic South Overturning Circulation represents a relevant regional component to the global thermohaline circulation. Monitoring the presence and physical characteristics (potential temperature, salinity) of the region\'s water masses is necessary to evaluate the variability of the region dynamics. In this context, chemical parameters (dissolved oxygen, phosphate, silicate and nitrate) are of great importance because, even when used as complementary tracers of water masses, they present temporal and spatial variations that are bigger than the physical parameters due to the biogeochemical processes. In coastal regions, with all reservations, nutrients can be used as complementary tracers, for example, silicate and phosphate were considered good indicators of Plata Plume Water (PPW) and the nitrate for Central Atlantic South Water (SACW). In the offshore region were identified by the physical parameters and complemented by the chemical parameters the already know water masses: Tropical Water (TW), SACW, Antarctic Intermediate Water (AAIW) (oxygen and nutrients maximum), Upper Circumpolar Deep Water (UCDW) and Lower Circumpolar Deep Water (LCDW) (oxygen minimum and nutrients maximum), North Atlantic Deep Water (NADW) (oxygen maximum and nutrients minimum) and Antarctic Bottom Water (AABW) (silicate maximum). In addition, nutrients can be used as tools to study the dynamics of the region. Along the transect close to 34.5 ° S, differences in physical and chemical parameters due to mixing processes can indicate changes in the circulation of water masses. The dissolved oxygen presented the largest differences between the east and west portions for the TW, AAIW, UCDW and NADW. The phosphate showed the process for the TW, UCDW and NADW. The silicate showed the remarkable variations for the AAIW, UCDW and NADW. And the nitrate presented homogeneous distribution, without variations that allow indicating changes in the circulation process in the region.

O coeficiente de reaeração constitui-se no principal parâmetro usado em modelos de qualidade na avaliação preventiva do efeito da descarga de resíduos orgânicos sobre a concentração do oxigênio dissolvido (OD) em cursos de água naturais. Na literatura os valores observados para a concentração de saturação de OD em procedimentos experimentais para a determinação das taxas de reaeração superficial são, geralmente, reportados como inferiores aos valores calculados para as condições de temperatura, salinidade e pressão em que os experimentos foram realizados. Esse fato interfere significativamente na determinação do coeficiente de reaeração superficial, K2. Avalia-se neste trabalho a hipótese de que nessas situações a água é exposta a uma fonte de OD, que é a superfície em contato com a atmosfera, mas também a um sumidouro de OD, criado pelo próprio sistema de movimentação do fluido. O modelo matemático amplamente utilizado para estes fins não considera essa última possibilidade. Neste estudo foi comparada a eficácia deste modelo com um que considera a existência sumidouros do OD, o que justifica a baixa estimativa da concentração de saturação deste gás. Observou-se uma forte correlação entre a pressão na linha de sucção do sistema de recirculação e o valor do coeficiente de desoxigenação K*3 , que quantifica a intensidade do sumidouro. / The reaeration coefficient constitutes the main parameter used in models for the quality assessment of the preventive effect of the discharge of organic wastes on the concentration of dissolved oxygen (DO) in natural waterways. In the literature the values observed for the saturation concentration of DO in experimental procedures for determining the surface reaeration rates are generally reported as lower than the values calculated for the conditions of temperature, salinity and pressure at which the experiments were performed. This interferes significantly in the determination of surface reaeration coefficient, K2. In this work the following hypothesis is evaluated: that in these situations the water is exposed to a source of DO, which is the surface in contact with the atmosphere, as well as an DO sink, created by the pumping system. The mathematical model widely used does not consider this possibility. In this study the two kind of models were compared and the reasons for divergence were looked upon. There was a strong correlation between the pressure drop in the suction line of the recirculation system and a pseudo-coefficient of deoxygenation K*3 , which quantifies the sink intensity.