Optical parameters measured via absorption spectroscopy and high-resolution fluorescence spectroscopy were used to characterize dissolved organic matter (DOM) in the springshed of Kings Bay, a spring-fed estuary located on Florida's Springs Coast. Over the past 40 years, springs supplying groundwater to Kings Bay have shown an increase in nitrate concentration. The overall goal of this project was to fingerprint wells and spring sites with elevated nitrogen concentrations using CDOM optical properties and establish relationships between nutrient and optical parameters. Samples were obtained from various sites: springs, Kings Bay surface (KBS), wells, coastal waters in and at the mouth of Crystal River (Coast) and lakes and rivers (LNR), during dry and wet seasons. The relationships between the environmental parameters and traditional optical parameters which provide insight into source characteristics were analyzed. Excitation emission matrix spectroscopy (EEMS) provided information about the concentration and chemical nature of organic matter in the study area. CDOM optical properties combined with salinity clearly separated the sources of fixed nitrogen in the Bay. Northern springs with elevated dissolved inorganic nitrogen (DIN) concentration had lower salinities and showed a presence of protein peaks. CDOM concentration was negatively correlated with total nitrogen (TN) and DIN, which suggests that these are subjected to anthropogenic influences. Humic peaks dominated the composition of the southern springs. CDOM concentrations were much higher than in the northern springs and there was a positive correlation between CDOM and both TN and DIN. These findings suggest that the fixed nitrogen in the southern springs is naturally occurring organic matter and the low concentrations may partially be a result of subsurface mixing of saltwater and freshwater in the aquifer. Thus, hypothesis testing showed that there was a significant difference between northern and southern springs Hypothesis testing also showed that there is a significant and unexpected positive relationship between CDOM and salinity studying Kings Bay, which is due to the low CDOM concentration in the springs discharging fresh water. This unique dataset also determined that the intercept of the mixing line was significantly different form zero. This indicates that CDOM is present and detectable at very low concentrations. Parallel Factor Analysis (PARAFAC) was used to evaluate CDOM composition from excitation emission matrix spectra (EEMs) and five components were identified: two humic, two marine humic, and one protein-like. The marine-like components, peak M, were produced in the marine environment and in meteoric groundwater. The study found a unique groundwater marker for coastal regions. Northern Kings Bay sites were characterized by a protein-like component, which has been associated with wastewater. Additional optical and environmental parameters were used in discriminate analysis, which successfully identified the CDOM markers for both natural and anthropogenic sources of nutrients in the environment. It is vital to improve the analysis of water, nutrients, and carbon from groundwater discharge into the coastal zone. Elevated DIN concentrations in groundwater are a widespread problem in Florida and over the past 30 years many spring waters have shown an increase in DIN concentrations. Nutrient discharge into delicate coastal areas can lead to ecological concerns. Investigating CDOM and nutrient distribution together can be a beneficial tool that can help differentiate sources from riverine/lacustrine, estuarine, marine, groundwater, and sewage impacted categories.

Tese(doutorado) - Universidade Federal do Rio Grande, Programa de Pós–Graduação em Oceanografia Biológica, Instituto de Oceanografia, 2012. / Submitted by Cristiane Gomides (cristiane_gomides@hotmail.com) on 2013-12-15T10:09:04Z No. of bitstreams: 1 karina.pdf: 8139075 bytes, checksum: c30bac487b6f4defadafc03c71b60d50 (MD5) / Approved for entry into archive by Sabrina Andrade (sabrinabeatriz@ibest.com.br) on 2013-12-18T17:52:30Z (GMT) No. of bitstreams: 1 karina.pdf: 8139075 bytes, checksum: c30bac487b6f4defadafc03c71b60d50 (MD5) / Made available in DSpace on 2013-12-18T17:52:30Z (GMT). No. of bitstreams: 1 karina.pdf: 8139075 bytes, checksum: c30bac487b6f4defadafc03c71b60d50 (MD5) Previous issue date: 2012 / A alta produtividade na zona costeira e na Plataforma Continental do Sul do Brasil é dada pelo aporte de nutrientes, os quais são determinantes para a produção primária. As regiões de plataforma (Santa Marta-SC 28,60ºS e Albardão-RS 33,20ºS) foram selecionadas por apresentarem características diferenciadas em relação à topografia, sazonalidade e dinâmica das massas de água. Sendo assim, essas possuem diferentes mecanismos de fertilização, além dos aportes continentais. A proximidade à zona de Convergência Subtropical (CST) é determinante para a produtividade dessas regiões, visto que: no inverno, a intrusão da Água Subantártica de Plataforma na região do Albardão aumenta consideravelmente as concentrações de nutrientes na região e; no verão, a Água Central do Atlântico Sul resultado da CST aflora na região de Santa Marta, sendo responsável por 60% da produção nova local. Além disso, aportes subterrâneos foram evidenciados tanto na zona costeira quanto na região de plataforma. No extremo sul do Brasil verificou-se, mediante a variação espaço-temporal de isótopos naturais de rádio e radônio, a ocorrência de advecção de água subterrânea ao longo de toda a costa, desde a desembocadura da Lagoa dos Patos até as proximidades do Uruguai (média: 2,17± 0,2 cm d-1). Com a aplicação de modelos pré-estabelecidos, foi possível calcular os fluxosde nutrientes para a zona costeira (NIT: 21 105 mol d-1) e avaliar o potencial produtivo relacionado a essas descargas (2800 gC m-2 ano-1). Desse modo, entende-se que a parcela de água subterrânea deva ser definitivamente incluída no balanço de massas da região, uma vez que apresenta um potencial produtivo de 7 a 32 vezes maior quando comparado às outras regiões onde a estimativa foi realizada. / High productivity on the coastal region and on the Southern Brazil Continental Shelf is provided by the nutrient input which is fundamental to primary productivity. The regions of Santa Marta, SC (28.60ºS) and Albardão, RS (33.20ºS) were selected due to their special characteristics regarding the topography, seasonality and dynamics of their water mass. Therefore, these areas have different fertilization mechanisms besides the continental input. The proximity to the subtropical convergence zone (SCZ) is determinant in relation to productivity because, in winter, the intrusion of the Subantarctic Shelf Water (SSW) in the Albardão region considerably increases the nutrient concentration whereas, in summer, the South Atlantic Central Water (SACW) that results from the SCZ, moves to the Santa Marta region and is responsible for 60% of the new local production. In addition, subterraneous input was observed both on the coastal areas and on the shelf. In southern Brazil, spatial - time variations of radionuclides (Ra e Rn) show the occurrence of groundwater advection along the coast, from the mouth of Patos Lagoon to Uruguay rates (average: 2.17± 0.2 cm d - 1). Using mathematical models, it was possible to calculate the discharge of nutrients on the coastal zone (TIN: 21105 mol d - 1) and evaluate the productive potential regarding the Submarine Groundwater Discharge (2800 gC m - 2 y - 1). Thus, this study suggests that the portion of ground water should definitely be included in the mass budget of the region, since its productive potential is 7 to 32 times higher by comparison with other regions where this estimate was also carried out.