Made available in DSpace on 2014-12-17T15:42:03Z (GMT). No. of bitstreams: 1 MariaFPV.pdf: 6083202 bytes, checksum: 8b9199df5753800b615ab0a90bae3e8e (MD5) Previous issue date: 2007-12-10 / Heavy metals can cause problems of human poisoning by ingestion of contaminated food, and the environment, a negative impact on the aquatic fauna and flora. And for the presence of these metals have been used for aquatic animals biomonitoramento environment. This research was done in order to assess the environmental impact of industrial and domestic sewage dumped in estuaries potiguares, from measures of heavy metals in mullet. The methods used for these determinations are those in the literature for analysis of food and water. Collections were 20 samples of mullet in several municipality of the state of Rio Grande do Norte, from the estuaries potiguares. Were analyzed the content of humidity, ash and heavy metals. The data were subjected to two methods of exploratory analysis: analysis of the main components (PCA), which provided a multivariate interpretation, showing that the samples are grouped according to similarities in the levels of metals and analysis of hierarchical groupings (HCA), producing similar results. These tests have proved useful for the treatment of the data producing information that would hardly viewed directly in the matrix of data. The analysis of the results shows the high levels of metallic species in samples Mugil brasiliensis collected in Estuaries /Potengi, Piranhas/A?u, Guara?ra / Papeba / Ar?s and Curimata? / Os metais pesados podem provocar problemas de intoxica??o humana pela ingest?o de alimentos contaminados e para o meio ambiente, uma repercuss?o negativa ? fauna e flora aqu?ticas. E para detectar a presen?a destes metais t?m-se utilizado animais aqu?ticos para o biomonitoramento ambiental. Esta pesquisa foi feita com o intuito de se avaliar o impacto ambiental de esgotos dom?sticos e industriais despejados nos estu?rios potiguares, a partir das medidas de metais pesados em tainha. Os m?todos utilizados para estas determina??es s?o aqueles constantes da literatura para an?lise de alimentos e de ?gua. Foram coletas 20 amostras de tainha em diversos munic?pios do Estado do Rio Grande do Norte, oriundas dos estu?rios potiguares. Foram analisados os teores de umidade, cinzas e metais pesados. Os dados foram submetidos a dois m?todos de an?lises explorat?rios: an?lise de componentes principais (PCA), que proporcionou uma interpreta??o multivariada, mostrando que as amostras s?o agrupadas de acordo com as similaridades de teores de metais e an?lise hier?rquica de agrupamentos (HCA), produzindo resultados semelhantes. Estas an?lises mostraram-se ?teis para o tratamento dos dados produzindo informa??es que dificilmente seriam visualizados diretamente na matriz de dados. A an?lise dos resultados mostra os altos teores de esp?cies met?licas em amostras coletadas em tainhas nos Estu?rios Potengi, Piranhas/A?u, Guara?ra/Papeba/Ares e Curimata?

Este estudo tem como objetivo estudar o fósforo total e as especiações de fósforo nos sedimentos superficiais associados aos processos biogeoquímicos em dois sistemas estuarinos, na plataforma continental sudeste e na região polar antártica. Amostras de água de fundo foram coletadas em dois períodos sazonais (verão-inverno) nos estuários sob diferentes graus de impacto ambiental antrópico. A metodologia de extração das frações de (SEDEX) aplicada para obter as especiações químicas de fósforo foi testada com padrões certificados antes das análises. Os resultados foram reprodutivos e a eficiência da extração foi aceitável. As concentrações das espécies químicas de fósforo sedimentar nos dois estuários mostraram diferenças entre os setores seguindo as características granulométricas, influência da maré, condições redox das águas de fundo bem como, as ações antrópicas reveladas pelos dados quantitativos e qualitativos. Uma influência sazonal mínima foi observada. No caso da plataforma sudeste, altos valores de matéria orgânica foram observados em núcleos ao longo da plataforma, junto às estações externas das radiais de Santos e Ilha Grande mostrando uma diferenciação acompanhada pelas frações de fósforo orgânico e carbono orgânico. Nas demais radiais, altos valores de CaCO3 foram observados nas estações mais externas. Na Baía do Almirantado as frações predominantes foram P mineral, P detrítico, P-ligado à apatita autigênica, sendo que a forma orgânica foi baixa e associada a baixos valores de carbono orgânico. A quantificação e distribuição das espécies de fósforo nos sedimentos constituem importante ferramenta para compreender o ciclo biogeoquímico do fósforo e dos demais nutrientes nos ecossistemas marinhos. / This work aims to study the total and chemical species of phosphorus in the surface sediments associated to the biogeochemical processes in two estuarine systems, the southeastern continental shelf and Antarctic polar region. Bottom water samples were collected in two seasonal periods (summer-winter) in the estuaries under different degrees of environmental anthorpic impacts. The fraction extraction methodology (SEDEX) applied to obtain the chemical phosphorus species was tested in relation to the certified standards before analyses. The results were reproductive and the extraction efficiency was acceptable. The chemical species concentrations of sedimentary phosphorus in the two estuarine systems showed differences between sectors following the granulometric characteristics, tide influence, redox conditions of the bottom waters as well as anthropic actions revealed by quantitative and qualitative data. A minimum seasonal influence was observed. In the case of eastern continental shelf, high values of organic matter were found in nuclei distribution along the platform in the external stations of Santos and Ilha Grande radials showing a differentiation accompanied by organic phosphorus and C org., fractions. In the other radials high CaCO3 values were observed in the external stations. In the Admiralty Bay the predominant fractions were detrital apatite and authigenic/biogenic apatite, being that organic form was low, linked to low values of organic carbon. The quantification and distribution of P species in the sediments constitute important tools to understand the P and the other nutrient biogeochemical cycles in the sea ecosystems

River export has a strong influence on the productivity of coastal waters. During storm events, rivers deliver disproportionate amounts of nutrients and organic matter to estuaries. Anthropogenic changes to the land use/cover (LULC) and water use also have a strong influence on the export of nutrients and organic matter to estuaries. This study specifically addressed the following questions: 1) How does river water chemistry vary across LULC patterns in the Mission and Aransas river watersheds? 2) How do fluxes of water, nutrients, and organic matter in the rivers vary between base flow and storm flow? 3) How do variations in nutrient/organic matter concentrations and stable isotope ratios of particulate organic matter (POM) in Copano Bay relate to river inputs? Water was collected from the Mission and Aransas rivers and Copano Bay from July, 2007 through November, 2008 and analyzed for concentrations of nitrate, ammonium, soluble reactive phosphorus (SRP), dissolved organic nitrogen, dissolved organic carbon, particulate organic nitrogen, particulate organic carbon (POC), and the stable C and N isotope ratios of the POM. The first half of the study period captured relatively wet conditions and the second half was relatively dry compared to long term climatology. Riverine export was calculated using the USGS LOADEST model. The percentage of annual constituent export during storms in 2007 was much greater than in 2008. Concentration-discharge relationships for inorganic nutrients varied between rivers, but concentrations were much higher in the Aransas River due to waste water contributions. Organic matter concentrations increased with flow in both rivers, but POM concentrations in the Aransas River were two fold higher due to large percentages of cultivated crop land. Values of [delta]¹³C-POC show a shift from autochthonous to allochthonous organic matter during storm events. Following storm events in Copano Bay, increases and quick draw down of nitrate and ammonium concentrations coupled with increases and slow draw down of SRP illustrate nitrogen limitation. Organic matter concentrations remained elevated for ~9 months following storm events. The [delta]¹³C-POC data show that increased concentrations were specifically related to increased autochthonous production. Linkages between LULC and nutrient loading to coastal waters are widely recognized, but patterns of nutrient delivery (i.e. timing, duration, and magnitude of watershed export) are often not considered. This study demonstrates the importance of sampling during storm events and defining system-specific discharge-concentration relationships for accurate watershed export estimation. This study also shows that storm inputs can support increased production for extended periods after events. Consideration of nutrient delivery patterns in addition to more traditional studies of LULC effects would support more effective management of coastal ecosystems in the future. / text

The Isipingo River and Estuary system located in the province of KwaZulu-Natal, although relatively small, has been subjected to the impacts of intense development within the catchment. The catchment is characterized by informal and formal dwellings and intensive industrial activities in the lower catchment and in close proximity to the estuary. Significant modifications to the hydrology of the system has occurred as a result of the diversion of the Umlazi River (which previously merged with the Isipingo River at the estuary mouth), canalization of the lower portion of the Isipingo River flowing through the Prospecton Industrial Area and the development of the Diversion Works system (to regulate flows to the lower Isipingo River), removal of riparian vegetation, encroachment onto the river and estuarine floodplain, and land reclamation through the infilling of wetlands all of which has culminated in a deterioration of the functionality and health of this system. The main aspects of this study focus on water and sediment quality, material flux between the estuary and the sea and the management of the system. The water quality variables covered as part of this dissertation include physical, chemical (nutrients and heavy metals) and microbiological (faecal coliforms) components. The water quality of the river and estuary presents a risk to human health and the concentrations of heavy metals generally exceeded the South African Water Quality Guidelines that prescribes target levels, implying potential negative impacts to aquatic health. The Isipingo system exhibited signs of eutrophication with phosphorus concentrations in excess of the target level to prevent eutrophication. Excessive water hyacinth growth was visible during most of the field surveys. A geochemical assessment of heavy metals in surface sediments of the river and estuary was also undertaken. The results indicate that although the presence of several metals were undetectable at certain river sites, the concentrations of those heavy metals present increased in a longitudinal direction from the river to the estuary. The contamination factor analysis for all metals indicated low contamination except for selenium. The riverine sites yielded moderate enrichment by some heavy metals in both seasons. The degree of contamination for each site with the exclusion of selenium was low. The inclusion of selenium in the assessment raises the estuary to a considerably contaminated status in the wet season. The analysis suggests that the enrichment of the system by selenium is due to an anthropogenic source. The Geo-accumulation Index places the sediment in an overall unpolluted category. The study conducted on the net exchange of heavy metals and nutrients between the Isipingo Estuary and the adjacent marine environment (i.e. Indian Ocean) demonstrates that significant quantities of the suite of heavy metal analysed are exported on an annual basis while copper, nickel and zinc are imported into the estuary. Significant quantities of ammonia and nitrates are exported annually from the Isipingo Estuary while a net annual import of phosphorous is observed. The variation in the quantity and concentration of nutrients exported during the seasons may be attributed to anthropogenic source. The import of nutrients from marine sources can accumulate in the estuary and contribute to eutrophication of the Isipingo Estuary. This study also demonstrated that although the ebb flow has a much longer duration than the flood flow, the flood velocities observed were generally greater than the ebb velocities. The final part of this research identifies other environmental problems experienced in the Isipingo catchment. The following issues are identified as directly or indirectly contributing to stress and deterioration of the water quality of the Isipingo system: reduction in water quantity, poor water quality, moderate enriched sediment, loss of habitat integrity, species diversity and invasive alien vegetation and uncontrolled solid waste. A Water Quality Management Plan including management objectives, strategies and action plans to address the direct and indirect factors influencing the system are proposed. A water quality monitoring program is also proposed for the Isipingo River and Estuary. The adoption and execution of the water quality management plan and monitoring program will assist in the prevention of further degradation of the system and will be a stepping stone toward improvement. / Thesis (M.Sc.)-University of KwaZulu-Natal, Westville, 2013.

This study assessed the importance of overwash and breaching events on the ichthyofaunal community structure in the medium-sized temporarily open/closed Mpekweni Estuary located on the southeast coastline of southern Africa. The fish in the littoral zone of the estuary were sampled using a 5m seine net while the channel region was sampled using two nets, a smaller meshed 30m seine net to target the estuarine spawning species and the juvenile estuarine-dependant marine spawners, and a larger meshed 50m seine net to target the larger marine and freshwater spawning species. Intensive monthly sampling over two years provided data on selected physico-chemical and biological parameters. During the two year sampling period from November 2005 to October 2007 the estuary breached in late July 2006 and remained open till the sandbar re-formed across the mouth in late December 2006. Thus, sampling encompassed three open/closed phases 1) initial closed period, 2) open period and 3) re-closed period after the berm was re-formed. The open period was divided into two phases 1) the out-flow phase and 2) the tidal phase. A total of 36 fish species representing 19 families were sampled using the various seine nets employed during the investigation. In the littoral zone, the estuarine spawners (Estuarine Utilisation Category, [EUC] I), mainly the Gobiidae, Glossogobius callidus, dominated the samples numerically and by biomass. The smaller estuarine spawning species sampled in the channel were numerically dominated by Gilchristella aestuaria in conjunction with two other EUC I species, Atherina breviceps and G. callidus. The estuarine-dependant marine spawners (EUC II), however, dominated the ichthyofaunal biomass of the channel. The abundance and biomass of the larger species targeted were dominated by estuarine-dependant marine spawning species (EUC II), principally Rhabdosargus holubi. During the closed periods of the estuary, total fish abundance and biomass displayed weak seasonal patterns. The breaching event and subsequent open period was associated with a decrease in the total abundances of fish in the littoral zone and channel of the estuary, reflecting the out-flow of estuarine biomass-rich water into the marine environment. The breaching event coincided with a shift in the community composition of the ichthyofauna, reflecting the recruitment of marine spawning species into the estuary. Numerical analysis identified two distinct spatial fish communities within the estuary, a community associated with the mouth region and one comprising the rest of the estuary. The absence of any further spatial patterns in the ichthyofaunal community structure within the Mpekweni Estuary appear to be ascribed to the virtual absence of horizontal patterns in physico-chemical and biological parameters recorded in the system. Cohort analyses were employed to determine possible recruitment events for selected estuarine and marine spawning species. The estuarine spawning species displayed continuous recruitment patterns throughout the study, which appeared to be unaffected by the breaching event. Conversely, the larger marine spawning species displayed multiple cohorts, indicating non-continuous recruitment. Subsequent retrospective analysis of cohorts for the different species identified summer recruitment peaks that coincided with the breaching event and open period. Minor recruitment of marine spawning species also occurred during overwash events. The recruitment of ichthyofauna into the estuary was quantified during three distinct hydrological events: overwash, out-flow phase immediately after breaching and tidal phase during the period when the mouth was open. Estimates of fish recruitment were highest during the outflow phase immediately after the estuary breached and declined as the estuary became tidally inundated with marine water. Although not as high as the outflow and tidal phases, recruitment was evident during overwash events. Results of the current study highlight the importance of both breaching and overwashing events in structuring the ichthyofaunal community composition in a medium-sized southern African temporarily open/closed estuary. These results are broadly in agreement with similar studies conducted both locally and in other regions of the world.

Este estudo tem como objetivo estudar o fósforo total e as especiações de fósforo nos sedimentos superficiais associados aos processos biogeoquímicos em dois sistemas estuarinos, na plataforma continental sudeste e na região polar antártica. Amostras de água de fundo foram coletadas em dois períodos sazonais (verão-inverno) nos estuários sob diferentes graus de impacto ambiental antrópico. A metodologia de extração das frações de (SEDEX) aplicada para obter as especiações químicas de fósforo foi testada com padrões certificados antes das análises. Os resultados foram reprodutivos e a eficiência da extração foi aceitável. As concentrações das espécies químicas de fósforo sedimentar nos dois estuários mostraram diferenças entre os setores seguindo as características granulométricas, influência da maré, condições redox das águas de fundo bem como, as ações antrópicas reveladas pelos dados quantitativos e qualitativos. Uma influência sazonal mínima foi observada. No caso da plataforma sudeste, altos valores de matéria orgânica foram observados em núcleos ao longo da plataforma, junto às estações externas das radiais de Santos e Ilha Grande mostrando uma diferenciação acompanhada pelas frações de fósforo orgânico e carbono orgânico. Nas demais radiais, altos valores de CaCO3 foram observados nas estações mais externas. Na Baía do Almirantado as frações predominantes foram P mineral, P detrítico, P-ligado à apatita autigênica, sendo que a forma orgânica foi baixa e associada a baixos valores de carbono orgânico. A quantificação e distribuição das espécies de fósforo nos sedimentos constituem importante ferramenta para compreender o ciclo biogeoquímico do fósforo e dos demais nutrientes nos ecossistemas marinhos. / This work aims to study the total and chemical species of phosphorus in the surface sediments associated to the biogeochemical processes in two estuarine systems, the southeastern continental shelf and Antarctic polar region. Bottom water samples were collected in two seasonal periods (summer-winter) in the estuaries under different degrees of environmental anthorpic impacts. The fraction extraction methodology (SEDEX) applied to obtain the chemical phosphorus species was tested in relation to the certified standards before analyses. The results were reproductive and the extraction efficiency was acceptable. The chemical species concentrations of sedimentary phosphorus in the two estuarine systems showed differences between sectors following the granulometric characteristics, tide influence, redox conditions of the bottom waters as well as anthropic actions revealed by quantitative and qualitative data. A minimum seasonal influence was observed. In the case of eastern continental shelf, high values of organic matter were found in nuclei distribution along the platform in the external stations of Santos and Ilha Grande radials showing a differentiation accompanied by organic phosphorus and C org., fractions. In the other radials high CaCO3 values were observed in the external stations. In the Admiralty Bay the predominant fractions were detrital apatite and authigenic/biogenic apatite, being that organic form was low, linked to low values of organic carbon. The quantification and distribution of P species in the sediments constitute important tools to understand the P and the other nutrient biogeochemical cycles in the sea ecosystems

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Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2016-09-21T18:16:41Z No. of bitstreams: 1 Tese de Doutorado Luiz C. Cotovicz Jr. Versão Uff.pdf: 4982585 bytes, checksum: 7a9441ed4aef2fa1871fcee50e7e53c4 (MD5) / Made available in DSpace on 2016-09-21T18:16:41Z (GMT). No. of bitstreams: 1 Tese de Doutorado Luiz C. Cotovicz Jr. Versão Uff.pdf: 4982585 bytes, checksum: 7a9441ed4aef2fa1871fcee50e7e53c4 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências - Geoquímica. Niterói, RJ / As taxas de produção, transformação, emissão e sedimentação de carbono na interface terra-mar são significantes globalmente, porém pobremente quantificadas nas regiões tropicais. O aumento acelerado nas concentrações atmosféricas de dióxido de carbono (CO2) e metano (CH4) alerta a importância do monitoramento e quantificação das concentrações e fluxos desses gases do efeito estufa na zona costeira. A redação da presente tese foi separada em capítulos. Os capítulos 1 e 2 apresentam a introdução geral do trabalho e o estado da arte do conhecimento da temática da tese, sobre a dinâmica de CO2 e CH4 em estuários. O capítulo 3 contém a descrição do sistema de medição contínua e on-line da pressão parcial do CO2 (pCO2) e comparações entre as medições contínuas com estimativas indiretas calculadas a partir da alcalinidade total (AT) e pH da água em dois estuários contrastantes: a Baía de Guanabara, Rio de Janeiro, e o estuário do Rio São Francisco, AL. Na Baía de Guanabara, um estuário dominado pela forçante marinha e altamente impactado por atividades antrópicas, os valores calculados e medidos da pCO2 mostraram excelente concordância (R2 = 0.95, p < 0.0001). Em contraste, no estuário do Rio São Francisco, onde o gradiente salino completo foi amostrado, importantes superestimativas foram verificadas nos valores calculados em algumas amostras de água doce. A superestimativa média foi de 72%, chegando ao valor extremo de 737%. Esses erros foram atribuídos à contribuição da alcalinidade orgânica e à baixa capacidade de tamponamento do sistema carbonato sob condições de água doce, de baixo pH e baixa AT. Os capítulos 4 e 5 apresentam os resultados das variações temporais e espaciais nas concentrações e fluxos de CO2 e CH4 na interface água-atmosfera na Baía de Guanabara. O estudo foi conduzido entre Abril de 2013 e Abril de 2014 com monitoramento contínuo da pCO2, temperatura, salinidade, fluorescência e oxigênio dissolvido (OD). Amostragens discretas foram realizadas para CH4, clorofila a e nutrientes inorgânicos dissolvidos. As concentrações anuais de CO2 e CH4 variaram entre 22-3715 ppmv e 18-10350 nmol L-1, respectivamente. Marcantes subsaturações da pCO2 na água em relação à pCO2 atmosférica foram prevalentes em águas rasas, confinadas e termicamente estratificadas principalmente no verão, enquanto supersaturação foi restrita às proximidades da desembocadura de rios poluídos e efluentes de esgotos. O CO2 também apresentou variações diuturnas em função dos processos de fotossíntese e respiração, com maiores valores no período noturno. O CH4 apresentou sobressaturação em todas as amostras, com as concentrações mais altas próximas de localidades com maior influência antrópica. A produção de metano pareceu ser pequena na região amostrada em função da competição com a redução de sulfato, sendo a maior parte do CH4 sustentada por fontes alóctones (rios poluídos e esgoto doméstico). Contrariamente à maioria dos sistemas estuarinos, a Baía de Guanabara foi considerada um sumidouro anual de CO2 em função da concomitância entre alta incidência de radiação fotossinteticamente ativa (PAR), estratificação térmica e alta disponibilidade de nutrientes, que promoveram grandes florações de fitoplâncton e autotrofia (metabolismo autotrófico de 52,1 mol C m-2 ano-1). Os fluxos de CO2 na interface água-atmosfera foram da ordem de -9,6 a -18,3 mol C m-2 ano-1. Os fluxos calculados de metano ficaram entre 0,20 e 0,35 mol C m-2 ano-1, e estão bem acima da média dos valores documentados em outros estuários mundiais, mostrando que a poluição pode ser um importante fator nas emissões estuarinas. Dessa forma, a eutrofização pareceu amplificar o sumidouro de CO2, enquanto a poluição orgânica pareceu amplificar a emissão de CH4. Comparando os fluxos de CO2 e CH4 em termos de emissões equivalentes de CO2 (CO2-eq), as emissões de CH4 reduziram o caráter sumidouro do CO2 em aproximadamente 16%. Esses resultados indicam que mais estudos são necessários em regiões estuarinas tropicais cobrindo diferente tipologias, pois a maioria dos trabalhos publicados até o momento se concentraram em estuários temperados e dominados por rios. / The production, transformation, emission and burial of carbon at the land-ocean interface are globally significant, but rather poorly quantified in tropical regions. The increasing atmospheric concentrations of dioxide carbon (CO2) and methane (CH4) alerts to the importance and necessity of monitoring and quantifying the concentrations and fluxes of these greenhouse gases at coastal zone. The present doctoral thesis was divided into several chapters. Chapter 1 presents a general introduction to the thesis. Chapter 2 corresponds to a general introduction which focuses on the state of art of knowledge of the thesis subject, dealing with the CO2 and CH4 dynamics in estuaries. Chapter 3 describes the system applied for the online and continuous measurements of the aquatic partial pressure of CO2 (pCO2) and compares its estimate between the method of the continuous measurements with indirect estimates based on calculations with total alkalinity and pH in two contrasting Brazilian estuaries. One being the marine dominated and highly anthropogenically disturbed Guanabara Bay (State of Rio de Janeiro, SE-Brazil) and the other, the oligotrophic Sao Francisco River Estuary (State of Alagoas, NE-Brazil), impacted by dams. For Guanabara Bay, the measured and calculated pCO2 values showed an excellent agreement (R2 = 0.95, p < 0.0001). In contrast, the Sao Francisco estuary, showed good agreements between both methods in the estuarine mixing zone but not for it´s freshwater end member samples, which yielded substantial overestimations for the calculated pCO2. The average overestimation was 72%, reaching 737%. These discrepancies were attributed to the interference of organic alkalinity in the calculations particular in acid, poorly buffered freshwaters. Chapters 4 and 5 correspond to the part of this study, addressing the results of the temporal and spatial variations of CO2 and CH4 concentrations and atmospheric exchanges in Guanabara Bay. The study was conducted between April 2013 and April 2014, with continuous on line monitoring along trajectories of pCO2, temperature, salinity, fluorescence and dissolved oxygen. In addition, discrete sampling was performed at fixed stations along the trajectories for CH4, Chlorophyll a and dissolved inorganic nutrients. The annual concentrations of CO2 and CH4 ranged between 22-3715 ppmv and 18-10350 nmol L-1, respectively. Marked undersaturations of pCO2 were prevalent in shallow, confined and stratified waters especially at summertime, whereas oversaturations were restricted to the vicinity of the polluted river mouths and effluent discharge. The CO2 presented diurnal variations related to the processes of photosynthesis and respiration, with higher values at nigh-time period. CH4 was oversaturated in all samples, with higher concentrations primarily in the polluted regions. Methanogenesis seemed to be low in the sampled regions due to the competition with sulphate-reduction, with the major part of the CH4 sustained by allochthonous sources, derived from the sewage network. In contrast to the major part of the world´s estuarine systems, Guanabara Bay was considered a strong sink of CO2 due to concomitant effects of high photosynthetically active radiation intensity (PAR), thermal stratification and net autotrophy (autotrophic metabolism of 52.1 mol C m-2 yr-1). The air-water CO2 fluxes were between -9.6 and -18.3 mol C m-2 yr-1. The calculated methane emissions were between 0,20 and 0,35 mol C m-2 yr-1, and were well-above of the world-average documented for other estuarine systems, showing that pollution can be an important factor in coastal CH4 emissions. As such, eutrophication seemed to amplify the CO2 sink, whereas the organic pollution seemed to amplify the CH4 emissions. Comparing the CO2 and CH4 in terms of CO2 equivalent emissions (CO2-eq), emissions of CH4 reduced the CO2 sink by about 16%. These results indicate that studies of topical estuaries covering different types of systems need to be enhanced, as most part of studies were conducted in river-dominated and temperate estuaries.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-05-09T16:04:57Z No. of bitstreams: 1 Dissertação Mestrado Raphael Pietzsch.pdf: 4110966 bytes, checksum: df24bdc5f7c697ce89fe6793eab5f517 (MD5) / Made available in DSpace on 2017-05-09T16:04:57Z (GMT). No. of bitstreams: 1 Dissertação Mestrado Raphael Pietzsch.pdf: 4110966 bytes, checksum: df24bdc5f7c697ce89fe6793eab5f517 (MD5) / Conselho Nacional de Desenvolvimento Cientifico e Tecnológico / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / O presente estudo teve como objetivo analisar hidrocarb onetos policíclicos aromáticos (HPAs), em diversas seções de dois testemunhos de sedimentos recentes, no estuário de Guaratuba, Paraná, a fim de avaliar os possíveis impactos decorrentes da crescente ocupação humana ao redor e de suas atividades na região. Este sistema estuarino está situado dentro dos li mites de uma Área de Proteção Ambiental, um local considerado ainda rela tivamente preservado. Com esta finalidade, se buscou quantificar quatorze HPAs sele cionados nos testemunhos, de aproximadamente 40 cm cada, os quais foram coletados na parte interna – próxima à área de desembocadura dos principais rios da região, Cubatão e São João – e na parte mais externa, próxima à saída para o m ar. A identificação e quantificação destes hidrocarbonetos foi realizada empreg ando-se um cromatógrafo à líquido de alto desempenho (HPLC – “High Performa nce Liquid Chromatography”), acoplado a um detector de fluorescência. Além disso, busc ou-se quantificar o teor de matéria orgânica nestes sedimentos, para observar se pode ria haver uma correlação entre esta e os HPAs. A concentração total de HPAs encontr ada nas amostras variou de 1,5 a 3.272,1 ng·g -1 (mediana 364,2) de sedimento seco, o que coloca a baía de Guaratuba como um ambiente pouco poluído a moderadamente poluído, se comparada com outras regiões similares do globo. Na part e mais externa, uma tendência atual é parece ocorrer, em função de um crescen te acúmulo destes hidrocarbonetos no sedimento, nas seções mais superficiais. Esta área é a que sofre maior urbanização nas proximidades do estuário nas últim as décadas. As concentrações de HPAs são, contudo, menores do que na base , a qual apresenta as maiores concentrações. A partir disso, pode-se julgar qu e a região esteve sujeita a impactos consideráveis no passado sem, no entanto se demo nstrar alarmante no presente. Um nível dos sedimentos, registrado no interior da baía, em que diversos HPAs estão presentes, indica que houve pelo menos um mom ento de significativa contribuição de queimadas. Além disso, os dados sugerem qu e processos biogênicos ou a diagênese inicial podem ter uma parcel a de contribuição na produção natural de HPAs. / The present study aims to analyze polycyclic aromatic hydro carbons (PAHs) in several sections of two cores of recent sediments, from the Guaratuba estuary, Parana State, to evaluate the degree of impact in the area from increasing human occupation and activities. An Area of Environmental Preser vation encloses this estuarine system, a location considered still pristine. Fo urteen selected PAHs were analyzed. The cores had roughly 40 centimeters, one colle cted in the inner part of the estuary and the other in the outer section, close to the sea. The identification and quantification of theses hydrocarbons was conducted using a HPLC – High Performance Liquid Chromatography coupled to a fluore scence detector. Besides, the total organic matter was quantified in order to s ee if there was any correlation with the PAHs. The concentration of total PAHs ranged from 1.5 and 3272.1 ng·g -1 (median 364,2) dry weight, which characterizes Guaratub a bay between a low polluted to moderately polluted environment, when com pared to similar environments around the globe. In the outer sector of the estuary, a trend in the present days is observed, showing an increase in the concentration of these hydrocarbons in the surface sediments. The outer sector is also the area that has been experiencing the fastest urbanization process in recent decades. Despite of t hat, the PAH concentrations are lower than in the bottom, which has the highest concentrations. This suggests that the region has been subjected to consid erable impacts in the past, although it does not seem to be alarming in the pres ent times. Within a level of the sediment cores, recorded in the inner sector of the bay , several PAHs are present in higher concentrations, indicating that at least in one moment there was a contribution of forest fires. Besides that, the data also suggest tha t biogenic processes or early diagenesis may have a slightly contribution to the nat ural production of PAHs.