Die Untersuchung von Klimaszenarien ergab, dass die Grundwasserneubildung in Nordostdeutschland abnehmen könnte. Um Süßgewässer zu erhalten müssen neue Strategien entwickelt werden. Im Gebiet des Lietzengrabens wird Klarwasser eingeleitet, um Feuchtgebiete und Seen zu erhalten. Diese Strategie wurde durch eine Szenarioanalyse erarbeitet, die sich auf das hydrologische iterative Modell ArcEGMO-ASM stützte. In dieser Arbeit wurde das voll integrierte Modell HydroGeoSphere genutzt, um den Fluss von Wasser an der Oberfläche und im Untergrund zu simulieren. Basierend auf dieser Simulation wurden Fließpfade und Aufenthaltszeiten abgeschätzt. Die Ergebnisse beider Modelle wurden analysiert und verglichen. Mit beiden Modellen war es möglich, die Abfluss- und Grundwasserdynamiken im Einzugsgebiet zu reproduzieren. Bei der Anwendung von HydroGeoSphere fehlten Möglichkeiten zur Berücksichtigung von z.B. Schneefall und Wehren, welche in ArcEGMO-ASM vorhanden sind. Die Kalibrierung des Modells lieferte Parameterwerte, die eine Reproduktion der Dynamiken erlaubten. Allerdings könnte HydroGeoSphere nur eingeschränkt nutzbar sein, da die Werte teils unrealistisch waren. HydroGeoSphere ermöglichte aber die Abschätzung von unterirdischen Fließpfaden und Aufenthaltszeiten. Weiter wurde der Austritt von Grundwasser in einen Bachabschnitt durch Messungen bestimmt und mit Simulationsergebnissen verglichen. Keines der Modelle war geeignet, die räumlichen Muster auf dieser Skala zu reproduzieren. Die simulierten Exfiltrationsraten wichen von den beobachteten ab. Der Vergleich von ArcEGMO-ASM und HydroGeoSphere zeigte die Vorteile und Grenzen der Modelle auf. Der Einsatz von HydroGeoSphere bei Untersuchungen von Bewirtschaftungsstrategien macht sich noch nicht bezahlt, vergleicht man den Aufwand mit den Vorteilen. Da HydroGeoSphere weiterentwickelt wird und die Rechenkapazitäten zunehmen, könnte das Modell in der nahen Zukunft in der Praxis nutzbar sein. / Analysis of climatic scenarios for North-East Germany showed that groundwater recharge could decline. In order to sustain freshwaters, new strategies must be developed. At the Lietzengraben catchment treated wastewater is discharged to sustain wetlands and lakes in the catchment. This management strategy was developed previously by scenario analysis, performed by the hydrological iterative model ArcEGMO-ASM. In this work, the fully integrated model HydroGeoSphere was used to simulate the surface and subsurface water flow in the catchment. Based on the simulation results, flow paths and residence times were estimated. The results of the simulations by both models were investigated and compared. It was possible to reproduce the catchment dynamics regarding discharge and groundwater heads reasonably well with both models. The application of HydroGeoSphere was limited due to the inability of the model to represent features like snowfall and weirs, which are represented in ArcEGMO-ASM. The calibrated parameter values enabled the model to reproduce the catchment dynamics reasonably well. HydroGeoSphere may be limited in its use since the obtained values are partially unrealistic. HydroGeoSphere allowed the approximation of subsurface flow paths and residence times. The exfiltration of groundwater to a stream reach was estimated by measurements and compared to simulation results. Both models were not able to reproduce the spatial patterns on a sub-reach scale and the calculated exfiltration rates did not match the observed rates. The comparison of ArcEGMO-ASM and HydroGeoSphere showed the advantages and limitations of both models. Comparing the overall additional effort to the benefits, however, the application of HydroGeoSphere to investigations regarding management strategies or scenario analyses may not pay off. Since HydroGeoSphere is under steady development and computational resources improve, the use of HydroGeoSphere may be applicable in the near future.

Die Arbeit beinhalted verschiedene Studien, die die Grundwasser (GW)-Oberflächenwasser (OW)-Interaktion im Norddeutschen Tiefland untersuchen. Dabei werden zwei Ansätze verfolgt: der hydrogeologische und der limnologische Ansatz. Ersterer betrachtet die Interaktionen aus dem Blickpunkt der unterirdischen Wasserbewegung. Diese ist hauptsächlich gesteuert durch die Verteilung der hydraulische Leitfähigkeit (Sediment) und des hydraulischen Gradienten. Es ist immer noch eine Herausforderung beide Steuerungsgrößen richtig abzuschätzen. Mit neuen Ansätzen, welche auf der Wechselwirkung zwischen verschiedenen Landschafskomponenten basieren (Wasserstände, Topographie, Vegetation, Nährstoffe), wurde klein- bis mesoskalige Sedimentverteilungen in einer Aue untersucht und beschrieben. Des Weiteren konnte mit einem einfachen Grundwassermodell gezeigt werden, das verschiedene Grundwasserstonckwerke (regionale Skala) die Interaktion zwischen GW und einem See beeinflussen können. Der limnologische Ansatz basiert auf der Annahme, dass Bereiche in einem See identifiziert werden können an denen Grundwasser zutritt. In der vorliegenden Arbeit, wurden eine Methode getestet, die auf der unterschiedlichen Temperatur von beiden Wasserkörpern basiert: Im Frühjahr ist das GW wärmer als das Seewasser und sollte sich an der Seeoberfläche einschichten. Mittels thermalen Luftbildaufnahmen sollten somit Grundwasserzutritte identifizierbar sein. Die Studien aber zeigten, dass dies nur unter bestimmten Voraussetzungen möglich ist und seeinterne Prozesse bei der Interpretation der Temperaturverteilung an der Seeoberfläche berücksichtigt werden müssen. Somit besteht noch ein erhöhter Forschungsbedarf bezüglich des limnologischen Ansatzes. Dennoch birgt dieser ein großes Potential, denn er eröffnet die Möglichkeit kurzfristig auf grundwasserbürtige Einträge in OW direkt an der Sediment-Wasser-Grenze zu reagieren und verschafft somit Zeit für aufwändigere hydrogeologische Untersuchungen. / The thesis constists of different studies, which are investigating groundwater-surface water interaction in North-German-Lowlands. Therefore, two different approaches were used: the hydrogeological and the limnological one. The former is based on the classical hydrogeological point of view: the subsurface water movement is mainly driven by hydraulic conductivity (sediment) and the hydraulic gradient. However, the characterisation of both is still a challange. Different methods were used to characterize small- and meso-scale sediment distributions within a lowland floodplain. These are based on the interactions of different landscape components (water level fluctuations, topography, vegetation, nutrient distributions). Furthermore, a simple groundwater model was set up to illustrate how regional groundwater flow impacts local groundwater-lake interactions. The limnological approach is based on the assumption that areas of groundwater exfiltration into a lake are detectable directly at the sediment-water interface. For this purpuse, it was assuemed that temperature differences between both water bodies could be used as follows: in spring the groundwater temperature is higher than that of lakes. Hence, the warmer groundwater float on the lake surface. That should be detectable by thermal infrared imaging. However, the studies could illustrate, that this is only true for specific conditions. Furthermore, lake internal processes need to be considered for interpreting temperature distributions at the lake surface. As a consequence, the limnological approach requires more research activities, since it gives the opportunity to initate short-term measures on groundwater inputs in surface waters. This would also guarantee larger time spans for time-consuming hydrogeological studies.

A aquicultura teve um aumento significativo em todo o mundo nos últimos anos. Muitas classes de antimicrobianos são usadas na aquicultura para o tratamento de infecções causadas por bactérias patogênicas. Entretanto, a contaminação do ambiente, do alimento e a ocorrência de resistência microbiana decorrentes da intensa utilização dos antimicrobianos são motivos de preocupação. Com o objetivo de se saber a ocorrência de antimicrobianos e possíveis formação de resistência microbiana em pisciculturas paulistas, um método rápido, sensível e simples de extração em fase sólida acoplada à cromatografia líquida e espectrometria de massas sequencial (SPE-LC-MS/MS), foi desenvolvido e validado para a determinação simultânea de 12 antimicrobianos (oxitetraciclina, tetraciclina, clortetraciclina, ciprofloxacina, enrofloxacina, sarafloxacina, norfloxacina, florfenicol, cloranfenicol, sulfatizol, sulfadimetoxina e sulfametazina) em água superficial e sedimento. Outro método, utilizando LC-MS/MS, foi elaborado para a determinação dos antimicrobianos em peixes. Paralelamente, também, foi avaliada a seleção de resistência microbiana dessas classes de antimicrobianos em peixe. Os antimicrobianos foram extraídos do sedimento com acetonitrila e tampão citrato, a fase orgânica foi eliminada e a purificação do extrato realizada com cartuchos SPE Strata SAX 500 mg Phenomenex. Os extratos de sedimento e as amostras de água (sem pré-tratamento) foram injetadas em um sistema analítico, pela primeira vez utilizado no Brasil, que consistia em uma pré-concentração com um amostrador automático equipado com um loop de 900 ?L, uma válvula usada para alternar entre os modos de carregamento ou eluição, duas bombas e um sistema de MS/MS. Os extratos de peixe foram purificados por filtração utilizando cartuchos Captiva ND. Sulfadimetoxina-d6 foi utilizado como padrão interno para aferir a precisão dos resultados. Os métodos desenvolvidos foram validados baseados na decisão da União Europeia 2002/657/CE. As amostras foram coletadas de 4 pisciculturas localizadas na represa da usina hidrelétrica de Ilha Solteira, Brasil. Foram feitas 4 amostragens no período de abril de 2013 a janeiro de 2014, totalizando 144 amostras de água, 144 de sedimento e 126 amostras de peixe. Resíduos de oxitetraciclina, tetraciclina e clortetraciclina foram encontrados em sedimentos e oxitetraciclina, tetraciclina e florfenicol foram identificados nas amostras de água e peixe; à medida que aumentava a distância dos tanques e o tamanho do peixe as quantidades encontradas nas amostras diminuíam. Isolou-se bactérias resistentes a quinolonas, tetraciclinas, sulfonamidas em 36 cepas e o índice de resistência múltipla a antibióticos (MAR), variou entre 0 e 0,86, ou seja, cepas sensíveis a 100% dos antimicrobianos testados e outras resistentes a 86%. De acordo com os resultados encontrados considera-se que ações mais restritivas são necessárias quanto ao uso intensivo de antibióticos na produção de peixes / The aquiculture has had a sharp increase worldwide in the last years. Many classes of antibiotics have been used in aquaculture to treat infections caused by a number of pathogenic bacteria. However, environmental and food contamination and bacterial resistance are the main concerns arisen by these intense uses. In order to know the occurrence of antibiotics and possible antimicrobial resistance in fish farms in São Paulo, a fast, sensitive, and simple on-line solid phase extraction to liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) was developed and validated for simultaneous assessment of 12 drugs (chloramphenicol, florfenicol, oxytetracycline, tetracycline, chlortetracycline, sulfadimethoxine, sulfathiazole, sulfamethazine, enrofloxacin, ciprofloxacin, norfloxacin, and sarafloxacin) in surface water and sediment. Another method using LC-MS/MS was elaborated to determine antibiotics in fish. In parallel, the selection of antimicrobial resistance of these classes of antibiotics in fish was evaluated. The antibiotics were extracted from sediment with acetonitrile and citric buffer, the organic phase was eliminated and the clean-up was made by Strata SAX 500 mg of Phenomenex. The water phase of sediment and water samples (without pre-treatment) was injected in the analytical system, which consisted of a pre-concentration with an automated liquid sampler fitted with a 900 ?L injection loop; a valve is used to switch between the load or elution modes, a pair of pumps and a MS/MS system, it is the first time that this system is used in Brazil. The fish extracts were cleaned by filtration by Captiva cartridges. Sulfadimethoxine-d6 was used as an internal standard to obtain more reliable results. The developed method was validated based in the European Union Decision 2002/657/EC. The samples were collected from 4 fish farms located in Ilha Solteira hydroelectric dam, Brazil. Four sampling were made in the period April/2013 until January/2014, totalizing 144 samples of water and sediment and 126 fish samples. Residues of oxytetracycline, tetracycline and chlortetracycline, were found in sediment and oxytetracycline, tetracycline, and florfenicol have been identified in water and fish samples, with increasing distance from the tanks and the size of the fishs the quantities of residue found in the samples decreased. Bacteria were resistant to quinolones, tetracyclines, sulfonamides in 36 strains and the multiple antibiotic resistance index (MAR) values ranged between 0 and 0.86, that is, strains with a sensitivity of 100% to the tested antimicrobials and others resistant of 86% to the tested antimicrobials. According to the results it is believed that more stringent measures are needed concerning the intensive use of antibiotics in fish production

O objetivo do estudo foi avaliar a qualidade da água superficial e sedimento do Rio Pardo, considerando a sazonalidade e as relações entre diferentes parâmetros, e estimar o risco à saúde humana derivado da exposição aos metais. A leitura dos parâmetros limnológicos foi realizada no momento da coleta (in situ). Os metais em água superficial e sedimento foram analisados por Espectroscopia de Emissão Óptica com Plasma Induzido. A análise parasitológica foi realizada pelo método de sedimentação espontânea, e para Cryptosporidium spp. e Giardia spp. foi utilizado o Método Cryptosporidium and Giardia in Water by Filtration/IMS/FA (USEPA 1623). Já a quantificação bacteriana foi realizada por meio da técnica dos Tubos Múltiplos com Substrato Cromogênico. Para a avaliação de risco à saúde humana pela exposição aos metais presentes na água superficial foi considerado um cenário domiciliar, de acordo com o United States Department of Energy (USDOE) e a United States Environmental Protection Agency (USEPA). As técnicas foram realizadas no Laboratório de Ecotoxicologia e Parasitologia Ambiental (LEPA) da Escola de Enfermagem de Ribeirão Preto / USP, e no Laboratório de Salud Medio Ambiental y Toxicología da Universidad Rovira i Virgili, Espanha. Alguns parâmetros limnológicos (pH e Oxigênio Dissolvido) apresentaram valores acima dos estabelecidos pela Resolução CONAMA No 357/2005, assim como a avaliação bacteriológica. A análise parasitológica mostrou a presença de Entamoeba coli, Hymenolepis diminuta, Strongyloides stercoralis, Giardia spp. e Cryptosporidium spp. Em comparação aos padrões de qualidade estabelecidos pelo CONAMA No 357/2005, as concentrações dos metais analisados na água superficial estão em conformidade com a legislação brasileira. Os resultados das análises dos sedimentos mostraram que todos os metais apresentaram as médias das concentrações de acordo com os padrões estabelecidos pela Resolução CONAMA Nº 344/2004, embora Cu e Cr tenham apresentado, em alguns pontos de coleta, concentrações superiores às estabelecidas para o nível 1. A avaliação de risco para a saúde humana derivada da exposição aos metais indicou que a água do Rio Pardo pode apresentar risco para elementos não carcinogênicos (As, Cd, Cr IV, Cu, Mn, Ni, Tl, Sn, V and Zn), enquanto que os valores para os elementos carcinogênicos (As) estão de acordo com os riscos aceitáveis. PCA e HCA foram aplicadas permitindo identificar variações espaciais e sazonais causadas por fatores naturais e antropogênicos, além das associações entre as variáveis. Os resultados sugerem que a qualidade das águas e sedimento do Rio Pardo é afetada por fatores naturais e antropogênicos, incluindo a estrutura geológica, mineralogia, precipitação e escoamento superficial, assim como crescimento dos espaços urbanos com consequente aumento da população e incremento de processos de industrialização regional. Há uma clara tendência de crescimento da população nas proximidades do Rio Pardo, bem como das atividades econômicas, com consequentes impactos sobre os recursos hídricos. Frente a essa realidade, que estabelece um aumento na demanda de fontes de água para consumo da população, tem-se como possibilidade estratégica para o futuro o uso desse corpo d\'água para o abastecimento público de Ribeirão Preto e de outros municípios banhados pelo Rio Pardo, o que evidencia a importância deste estudo / The aim of the study was assess the quality of surface water and sediment of Pardo River, taking into account the seasonality and the relation among different parameters, and estimate the risk assessment to human health derived from exposure to metals. All measurements of limnological parameters were performed at the sampling time (in situ). Metals in surface water and sediment were analyzed by inductively coupled plasma spectrometry. The parasitological analysis was performed by the sedimentation method, and Cryptosporidium spp. and Giardia spp. by Cryptosporidium and Giardia in Water by Filtration/IMS/FA (USEPA 1623). Bacterial quantifications were carried out using the multiple tube technique with a defined substrate. The risk assessment to human health from exposure to metals was assessed under a residential scenario according to the United States Department of Energy (USDOE) and United States Environmental Protection Agency (USEPA). The techniques were performed at the Laboratory of Ecotoxicology and Environmental Parasitology (LEPA) at the Ribeirão Preto College of Nursing in the University of São Paulo (USP), and the metals analysis at the Laboratorio de Salud Medio Ambiental y Toxicología of the Universidad Rovira i Virgili, Spain. Dissolved oxygen and pH showed higher values than those set by CONAMA Resolution No 357/2005, as well as bacteriological evaluation. The parasitological analysis showed the presence of Entamoeba coli, Strongyloides stercoralis, Hymenolepis diminuta, Giardia spp. and Cryptosporidium spp. The levels of analyzed metals in surface water are in accordance to the Brazilian legislation (CONAMA No 357/2005). The results of sediments showed that all the metals had mean concentrations in accordance to brazilian legislation, but Cu and Cr presented in some points higher levels than those set by CONAMA No 344/2004 for level 1. The risk assessment to human health derived from exposure to metals indicated that the Pardo River can be a pathway of concern for human exposures to metals for non-carcinogens elements (As, Cd, Cr IV, Cu, Mn, Ni, Tl, Sn, V and Zn), while the values for carcinogenic (As) elements were in accordance to acceptable lifetime risks. PCA and HCA were applied in order to identify spatial and seasonal variations caused by natural and anthropogenic factors, in addition to associations among variables. The results suggest the quality of water and sediment from the Pardo River is affected by natural and anthropogenic factors, including the geology, mineralogy, rainfall and runoff, as well as growth of urban areas with a consequent population increases and industrialization processes. There is a clear trend of population and economic activities growth in the Pardo River area that makes the water of the Pardo River a strategic alternative for the future supply, which highlights the importance of this study

O projeto consistiu em avaliar o emprego de polímeros catiônicos e aniônicos de diferentes pesos moleculares como auxiliares de filtração no tratamento de águas de abastecimento proveniente de mananciais com alto grau de eutrofização com vistas a possibilitar a otimização da remoção de material particulado e minimização da evolução da perda de carga. O aparato experimental é composto, principalmente, por 4 filtros em escala piloto de alta taxa do tipo camada profunda e fluxo descendente por gravidade operados em paralelo. Os filtros possuem 5 m de altura e diâmetro interno de 150 mm. O procedimento experimental foi dividido em três etapas, execução de ensaios de fluidificação e expansão do leito dos filtros e utilização de polímeros catiônicos e de polímero aniônico como auxiliares de filtração. A primeira etapa teve como objetivo definir parâmetros de dimensionamento do sistema de lavagem em contra-corrente com ar e água e nas duas etapas seguintes foram realizados os ensaios de filtração a uma taxa de 500 m³/m²/dia, com a utilização dos polímeros com três dosagens diferentes. Os polímeros utilizados foram CA-2577, CA-2581, CD-2592 e N1986. Estes possuem estrutura e pesos moleculares variáveis, de forma que o trabalho tivesse uma maior amplitude. Os valores médios de turbidez, para a primeira etapa dos ensaios de filtração, foram de 2,36 ± 0,28 UNT e 1,12 ± 0,21 UNT para água bruta e decantada, respectivamente, 0,26 ± 0,07 UNT para o filtro F1 com antracito, 0,25 ± 0,08 UNT para o filtro F3 com antracito e adição de polímero, 0,29 ± 0,08 UNT para o filtro F2 com areia e 0,26 ± 0,08 UNT para o filtro F4 com areia e adição de polímero. Para a segunda etapa dos ensaios de filtração os valores médios de turbidez foram de 2,03 ± 0,36 UNT para água bruta, 0,80 ± 0,21 UNT para água decantada, 0,09 ± 0,03 UNT para o filtro F1, sem adição de polímero, e 0,15 ± 0,04, 0,16 ± 0,03 e 0,10 ± 0,04 UNT para os filtros F2, F3 e F4, respectivamente, todos com adição de polímero. Os resultados experimentais possibilitaram concluir que a adoção do antracito como material filtrante do tipo camada única e profunda apresenta a vantagem de permitir uma menor velocidade ascensional de água de lavagem para uma determinada expansão quando comparado a um filtro de areia de idêntica granulometria. A aplicação dos polímeros catiônicos e do polímero aniônico como auxiliares de filtração não proporcionou para nenhuma dosagem utilizada melhora significativa no comportamento dos filtros. Uma eventual melhora ou piora foi insignificante e estava ligada à qualidade da água decantada. No que diz respeito à perda de carga, os filtros com antracito tiveram carreiras de filtração mais longas quando comparados com os de areia, independente da utilização dos polímeros. / The project was to evaluate the use of anionic and cationic polymers of different molecular weights as filter aids to treat drinking water treatment of surface water sources with high degree of eutrophication, particularly with regard to particulate matter removal optimization and head loss rate minimization. The experimental apparatus was composed of four pilot scale, deep bed, down flow rapid gravity filters, operated in parallel. The filter columns were 5 m high, had inner diameter of 150 mm. The experimental procedure was divided in three stages, conduction of media fluidization and media expansion tests and cationic and anionic polymers application as filter aid. The first stage aims was to define design parameters for the filter backwashing system with water and air and in the two next phases the tests were conducted at a filtration rate of 500 m³/m²/day, with the use of polymers with three different dosages. The polymers tested were CA- 2577, CA-2581, CD-2592 and N1986. They have different structure and molecular weights, thus making wider the array of possibilities tested. The average values of turbidity, for the first stage of testing filtration, were 2.36 ± 0.28 and 1.12 ± 0.21 NTU for raw and settled water, respectively, 0.26 ± 0.07 NTU to the filter F1 with anthracite, 0.25 ± 0.08 NTU for the filter F3 with anthracite and addition of polymer, 0.29 ± 0.08 NTU for the filter F2 with sand and 0.26 ± 0.08 NTU for the filter F4 with sand and the addition of polymer. For the second stage of testing of the filter values of turbidity were 2.03 ± 0.36 NTU for raw water, 0.80 ± 0.21 NTU for settled water, 0.09 ± 0.03 for the filter F1, without the addition of polymer, and 0.15 ± 0.04, 0.16 ± 0.03 and 0.10 ± 0.04 NTU for filters F2, F3 and F4, respectively, all with the addition of polymer. The experimental results led us to conclusion that the adoption of anthracite as single media in deep bed filtration presents the advantage of a lower ascent backwash water velocity for any given bed expansion as compared to deep bed filtration through sand with the same granulometric characteristic. Application of cationic and anionic polymers as filter aids did not lead to any significant improvement in the behavior of pilot scale filters, regardless of applied polymer dosage. Any eventual improvement or worsening was not significant and was closely related to the settled water quality. Regarding the head loss, the filters with anthracite had longer filtration careers when compared to sand, regardless the use of polymers.

O projeto consistiu em avaliar o emprego de polímeros catiônicos e aniônicos de diferentes pesos moleculares como auxiliares de filtração no tratamento de águas de abastecimento proveniente de mananciais com alto grau de eutrofização com vistas a possibilitar a otimização da remoção de material particulado e minimização da evolução da perda de carga. O aparato experimental é composto, principalmente, por 4 filtros em escala piloto de alta taxa do tipo camada profunda e fluxo descendente por gravidade operados em paralelo. Os filtros possuem 5 m de altura e diâmetro interno de 150 mm. O procedimento experimental foi dividido em três etapas, execução de ensaios de fluidificação e expansão do leito dos filtros e utilização de polímeros catiônicos e de polímero aniônico como auxiliares de filtração. A primeira etapa teve como objetivo definir parâmetros de dimensionamento do sistema de lavagem em contra-corrente com ar e água e nas duas etapas seguintes foram realizados os ensaios de filtração a uma taxa de 500 m³/m²/dia, com a utilização dos polímeros com três dosagens diferentes. Os polímeros utilizados foram CA-2577, CA-2581, CD-2592 e N1986. Estes possuem estrutura e pesos moleculares variáveis, de forma que o trabalho tivesse uma maior amplitude. Os valores médios de turbidez, para a primeira etapa dos ensaios de filtração, foram de 2,36 ± 0,28 UNT e 1,12 ± 0,21 UNT para água bruta e decantada, respectivamente, 0,26 ± 0,07 UNT para o filtro F1 com antracito, 0,25 ± 0,08 UNT para o filtro F3 com antracito e adição de polímero, 0,29 ± 0,08 UNT para o filtro F2 com areia e 0,26 ± 0,08 UNT para o filtro F4 com areia e adição de polímero. Para a segunda etapa dos ensaios de filtração os valores médios de turbidez foram de 2,03 ± 0,36 UNT para água bruta, 0,80 ± 0,21 UNT para água decantada, 0,09 ± 0,03 UNT para o filtro F1, sem adição de polímero, e 0,15 ± 0,04, 0,16 ± 0,03 e 0,10 ± 0,04 UNT para os filtros F2, F3 e F4, respectivamente, todos com adição de polímero. Os resultados experimentais possibilitaram concluir que a adoção do antracito como material filtrante do tipo camada única e profunda apresenta a vantagem de permitir uma menor velocidade ascensional de água de lavagem para uma determinada expansão quando comparado a um filtro de areia de idêntica granulometria. A aplicação dos polímeros catiônicos e do polímero aniônico como auxiliares de filtração não proporcionou para nenhuma dosagem utilizada melhora significativa no comportamento dos filtros. Uma eventual melhora ou piora foi insignificante e estava ligada à qualidade da água decantada. No que diz respeito à perda de carga, os filtros com antracito tiveram carreiras de filtração mais longas quando comparados com os de areia, independente da utilização dos polímeros. / The project was to evaluate the use of anionic and cationic polymers of different molecular weights as filter aids to treat drinking water treatment of surface water sources with high degree of eutrophication, particularly with regard to particulate matter removal optimization and head loss rate minimization. The experimental apparatus was composed of four pilot scale, deep bed, down flow rapid gravity filters, operated in parallel. The filter columns were 5 m high, had inner diameter of 150 mm. The experimental procedure was divided in three stages, conduction of media fluidization and media expansion tests and cationic and anionic polymers application as filter aid. The first stage aims was to define design parameters for the filter backwashing system with water and air and in the two next phases the tests were conducted at a filtration rate of 500 m³/m²/day, with the use of polymers with three different dosages. The polymers tested were CA- 2577, CA-2581, CD-2592 and N1986. They have different structure and molecular weights, thus making wider the array of possibilities tested. The average values of turbidity, for the first stage of testing filtration, were 2.36 ± 0.28 and 1.12 ± 0.21 NTU for raw and settled water, respectively, 0.26 ± 0.07 NTU to the filter F1 with anthracite, 0.25 ± 0.08 NTU for the filter F3 with anthracite and addition of polymer, 0.29 ± 0.08 NTU for the filter F2 with sand and 0.26 ± 0.08 NTU for the filter F4 with sand and the addition of polymer. For the second stage of testing of the filter values of turbidity were 2.03 ± 0.36 NTU for raw water, 0.80 ± 0.21 NTU for settled water, 0.09 ± 0.03 for the filter F1, without the addition of polymer, and 0.15 ± 0.04, 0.16 ± 0.03 and 0.10 ± 0.04 NTU for filters F2, F3 and F4, respectively, all with the addition of polymer. The experimental results led us to conclusion that the adoption of anthracite as single media in deep bed filtration presents the advantage of a lower ascent backwash water velocity for any given bed expansion as compared to deep bed filtration through sand with the same granulometric characteristic. Application of cationic and anionic polymers as filter aids did not lead to any significant improvement in the behavior of pilot scale filters, regardless of applied polymer dosage. Any eventual improvement or worsening was not significant and was closely related to the settled water quality. Regarding the head loss, the filters with anthracite had longer filtration careers when compared to sand, regardless the use of polymers.

A aquicultura teve um aumento significativo em todo o mundo nos últimos anos. Muitas classes de antimicrobianos são usadas na aquicultura para o tratamento de infecções causadas por bactérias patogênicas. Entretanto, a contaminação do ambiente, do alimento e a ocorrência de resistência microbiana decorrentes da intensa utilização dos antimicrobianos são motivos de preocupação. Com o objetivo de se saber a ocorrência de antimicrobianos e possíveis formação de resistência microbiana em pisciculturas paulistas, um método rápido, sensível e simples de extração em fase sólida acoplada à cromatografia líquida e espectrometria de massas sequencial (SPE-LC-MS/MS), foi desenvolvido e validado para a determinação simultânea de 12 antimicrobianos (oxitetraciclina, tetraciclina, clortetraciclina, ciprofloxacina, enrofloxacina, sarafloxacina, norfloxacina, florfenicol, cloranfenicol, sulfatizol, sulfadimetoxina e sulfametazina) em água superficial e sedimento. Outro método, utilizando LC-MS/MS, foi elaborado para a determinação dos antimicrobianos em peixes. Paralelamente, também, foi avaliada a seleção de resistência microbiana dessas classes de antimicrobianos em peixe. Os antimicrobianos foram extraídos do sedimento com acetonitrila e tampão citrato, a fase orgânica foi eliminada e a purificação do extrato realizada com cartuchos SPE Strata SAX 500 mg Phenomenex. Os extratos de sedimento e as amostras de água (sem pré-tratamento) foram injetadas em um sistema analítico, pela primeira vez utilizado no Brasil, que consistia em uma pré-concentração com um amostrador automático equipado com um loop de 900 ?L, uma válvula usada para alternar entre os modos de carregamento ou eluição, duas bombas e um sistema de MS/MS. Os extratos de peixe foram purificados por filtração utilizando cartuchos Captiva ND. Sulfadimetoxina-d6 foi utilizado como padrão interno para aferir a precisão dos resultados. Os métodos desenvolvidos foram validados baseados na decisão da União Europeia 2002/657/CE. As amostras foram coletadas de 4 pisciculturas localizadas na represa da usina hidrelétrica de Ilha Solteira, Brasil. Foram feitas 4 amostragens no período de abril de 2013 a janeiro de 2014, totalizando 144 amostras de água, 144 de sedimento e 126 amostras de peixe. Resíduos de oxitetraciclina, tetraciclina e clortetraciclina foram encontrados em sedimentos e oxitetraciclina, tetraciclina e florfenicol foram identificados nas amostras de água e peixe; à medida que aumentava a distância dos tanques e o tamanho do peixe as quantidades encontradas nas amostras diminuíam. Isolou-se bactérias resistentes a quinolonas, tetraciclinas, sulfonamidas em 36 cepas e o índice de resistência múltipla a antibióticos (MAR), variou entre 0 e 0,86, ou seja, cepas sensíveis a 100% dos antimicrobianos testados e outras resistentes a 86%. De acordo com os resultados encontrados considera-se que ações mais restritivas são necessárias quanto ao uso intensivo de antibióticos na produção de peixes / The aquiculture has had a sharp increase worldwide in the last years. Many classes of antibiotics have been used in aquaculture to treat infections caused by a number of pathogenic bacteria. However, environmental and food contamination and bacterial resistance are the main concerns arisen by these intense uses. In order to know the occurrence of antibiotics and possible antimicrobial resistance in fish farms in São Paulo, a fast, sensitive, and simple on-line solid phase extraction to liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) was developed and validated for simultaneous assessment of 12 drugs (chloramphenicol, florfenicol, oxytetracycline, tetracycline, chlortetracycline, sulfadimethoxine, sulfathiazole, sulfamethazine, enrofloxacin, ciprofloxacin, norfloxacin, and sarafloxacin) in surface water and sediment. Another method using LC-MS/MS was elaborated to determine antibiotics in fish. In parallel, the selection of antimicrobial resistance of these classes of antibiotics in fish was evaluated. The antibiotics were extracted from sediment with acetonitrile and citric buffer, the organic phase was eliminated and the clean-up was made by Strata SAX 500 mg of Phenomenex. The water phase of sediment and water samples (without pre-treatment) was injected in the analytical system, which consisted of a pre-concentration with an automated liquid sampler fitted with a 900 ?L injection loop; a valve is used to switch between the load or elution modes, a pair of pumps and a MS/MS system, it is the first time that this system is used in Brazil. The fish extracts were cleaned by filtration by Captiva cartridges. Sulfadimethoxine-d6 was used as an internal standard to obtain more reliable results. The developed method was validated based in the European Union Decision 2002/657/EC. The samples were collected from 4 fish farms located in Ilha Solteira hydroelectric dam, Brazil. Four sampling were made in the period April/2013 until January/2014, totalizing 144 samples of water and sediment and 126 fish samples. Residues of oxytetracycline, tetracycline and chlortetracycline, were found in sediment and oxytetracycline, tetracycline, and florfenicol have been identified in water and fish samples, with increasing distance from the tanks and the size of the fishs the quantities of residue found in the samples decreased. Bacteria were resistant to quinolones, tetracyclines, sulfonamides in 36 strains and the multiple antibiotic resistance index (MAR) values ranged between 0 and 0.86, that is, strains with a sensitivity of 100% to the tested antimicrobials and others resistant of 86% to the tested antimicrobials. According to the results it is believed that more stringent measures are needed concerning the intensive use of antibiotics in fish production

Post-remediation soil, ground and surface water monitoring is essential to assess the effectiveness of remediation efforts undertaken to eliminate or minimize the risk of pollution to human health and valuable ecosystems. In that regard, comparison of pollution levels pre- and post-remediation is an effective way of evaluating the effectiveness of the remediation techniques used. Thus, this study sought to measure concentrations of pollutants in the soil, ground and surface water post remediation in Steel Valley, Vanderbijlpark and compare them to concentration levels prior to remediation, as well as compare them to internationally accepted standards with respect to risk to humans and the environment. Water samples were collected from three locations within the study site, in both the dry and rainy seasons and their physio-chemical and organic properties were tested. Soil samples were collected from six different locations within the study site and analysed for metal concentrations. The data was compared against that of the Iron and Steel Corporation (ISCOR) Vanderbijlpark Environmental Master Plan (EMP), water and soil guidelines of the World Health Organization (WHO) as well as South African water and soil guidelines. The study found that groundwater is generally safe for domestic use but Aluminium (Al), Iron (Fe) and Manganese (Mn) concentrations were above South African water quality guideline levels – with their concentrations ranging from 0.54 to 0.91 mg/L, 1.01 to 1.86 mg/L and 0.24 to 0.53 mg/L respectively. There were no traces of organic pollution in the water samples. Soil samples had levels of Al ranging from 1106 mg/kg to 1 3621 mg/kg, Mn concentrations in the range of 202.8 to 966.4 mg/kg and Fe ranging from 1 1587 to 23 201 mg/kg. Thus, water and soil at the selected sites are safe in terms of physico-chemical and organic quality. Natural attenuation should be able, over time, to further reduce the levels of parameters that are currently above the target range. Thus, there has been considerable reduction in pollutant concentrations, but as this study was limited in scope, additional research is needed to verify the results. / Environmental Sciences / M. Sc. (Environmental Science)

L’anticipation et l’adaptation de nos sociétés aux bouleversements résultants du changement climatique sont aujourd’hui des questions majeures guidant les activités humaines et l’action publique. Néanmoins, la prévision reste un défi essentiel en raison des fortes incertitudes existantes et il est primordial de continuer à progresser dans la compréhension des mécanismes à l’origine de ces bouleversements. Au sein du cycle hydrologique, le réservoir de surface (incluant les lacs, les rivières et les plaines d’inondation) occupe une place importante car il est l’une des principales ressources en eau des écosystèmes et des populations. Or, la dynamique des stocks d’eau de surface est toujours mal connue aux échelles régionale et globale, du fait de l’absence de mesures pluriannuelles d’extension et de hauteur d’eau des zones inondées, et de la prise en compte limitée de ces variables dans les modèles hydrologiques et hydrodynamiques. La télédétection spatiale offre désormais la possibilité d’effectuer un suivi des stocks d’eau de surface en utilisant la complémentarité entre l’imagerie multi-spectrale, permettant de cartographier les étendues inondées, et l’altimétrie radar fournissant des séries temporelles de hauteur d’eau des hydro-systèmes continentaux. L’objectif de ma thèse est de tirer le meilleur parti de la complémentarité entre les différents types d’observations spatiales pour évaluer les ressources en eau du réservoir de surface et mesurer la dynamique des transferts d’eau des continents aux océans, et son impact sur la zone côtière en utilisant les concentrations de matières en suspension comme traceur des masses d’eau. Depuis le milieu des années 1990, la multiplication des missions multi-spectrales à moyenne résolution (< 1 km de résolution spatiale) et des altimètres radars à haute précision (comprise entre 10 et 30 cm) permet de réaliser un suivi hebdomadaire à mensuel des volumes d’eau de surface dans les grands bassins fluviaux. / The anticipation and adaptation of our societies to the upheavals resulting from climate change are today major issues guiding human activities and public action. Nevertheless, the forecast remains a key challenge because of the strong uncertainties that exist and it is essential to continue to progress in understanding the mechanisms behind these upheavals. Within the hydrological cycle, the surface reservoir (including lakes, rivers and floodplains) occupies an important place as it is one of the main water resources of ecosystems and populations. However, the dynamics of surface water stocks are still poorly known at the regional and global scales, due to the absence of multi-year measures of extension and water depth of the flooded areas, and the limited consideration of these variables in hydrological and hydrodynamic models. Satellite remote sensing now offers the possibility of monitoring surface water stocks by using the complementarity between multispectral imagery, allowing to map flooded areas, and the radar altimetry providing time series of water depths of continental hydro systems. The aim of my thesis is to make the most of the complementarity between the different types of spatial observations to evaluate the water resources of the surface reservoir and to measure the dynamics of water transfers between land and ocean, and its impact on the coastal zone using suspended particulate matter as tracer of water bodies. Since the mid-1990s, the multiplication of multispectral missions with medium resolution (<1 km of spatial resolution) and high-precision radar altimeters (between 10 and 30 cm) makes it possible to carry out weekly-to-monthly monitoring of volumes surface water in large river basins.

The continuous demand on new residential and economic areas of the modern society has to face up with problems posed by polluted sites related to former industrial activities, typically located in suburbs areas. These sites, known as brownfields, are often located nearby navigable rivers to facilitate transport operations of industrial manufacturing, which increase their potential environmental threat due to the possible migration of pollutants in groundwater to surface water bodies through groundwater discharge. In this context, the objective of this research, performed in the scope of the FP6-IP AquaTerra project, was to contribute to a better assessment of the risk of groundwater contaminant dispersion for a brownfield located next to the Meuse River (Belgium), in a context where strong groundwater - surface water interactions prevail. The brownfield of interest corresponds to the site of the former coke factory of Flémalle. Resulting from industrial activities, soil and groundwater located in the alluvial aquifer are heavily contaminated with various types of organic (BTEX, PAHs, mineral oils...) and inorganic (As, Zn, Cd...) pollutants. To do so, detailed characterisation campaign was performed, consisting of, on the one hand, classical field experiments such as pumping tests, injection tests and tracer experiments; on the other hand, advanced and original field experiments such as detailed monitoring of groundwater - surface water interaction and dynamics, and the development and application of an innovative tracer technique, the Finite Volume Point Dilution Method (FVPDM), used to quantify and monitor groundwater fluxes. Monitoring and field works data was subsequently used to develop and calibrate a groundwater flow model using the finite difference code MODFLOW, with an automatic parameter estimation approach based on an original combined regional scale (zonation) and local scale (pilot points) approach. A transport model was also developed using MT3DMS and calibrated using tracer experiments performed in the brownfield. This groundwater flow and transport model was used to better quantify the dynamics of groundwater - surface water interactions and to model various scenarios of contaminant dispersion through the aquifer - river system. For these scenarios, benzene was considered because it is one of the main pollutants encountered in the site, its large solubility and mobility in groundwater and its acute toxicity. These scenarios were established considering various groundwater flow conditions (steady state vs. transient) and various hydrodispersive processes possibly affecting the mobility of benzene in groundwater, namely advection, hydrodynamic dispersion, sorption - desorption and, as evidenced by the research results of the University of Neuchâtel (Switzerland), benzene degradation under sulphate reducing conditions. These simulations indicate that benzene attenuation is mainly controlled by ongoing benzene degradation processes, aquifer heterogeneity and river stage fluctuations. Based on this analysis, the risk of benzene dispersion is low, and monitored natural attenuation (MNA) is a valuable option with (1) monitoring benzene at control planes downstream from the sources; (2) further investigation on risk of sulphate depletion in the alluvial aquifer; and (3) further investigation on mobilisation/immobilisation of heavy metals related to dynamics of organic pollutant plumes.