Thesis (M. Tech. - (Civil Engineering, Faculty of Engineering and Technology))--Vaal University of Technology, 2010. / During the last few years, concern has been growing among many stakeholders all over the world about declining levels of surface water bodies accompanied by reduced water availability predominantly due to ever increasing demand and misuse. Furthermore, overexploitation of environmental resources and haphazard dumping of waste has made the little water remaining to be so contaminated that a dedicated rehabilitation/remediation of the environment is the only proactive way forward. River Rwizi Catchment is an environment in the focus of this statement. The overall objective of this research was to plan, restore and rationally allocate the water resources in any river basin with similar attributes to the study area. In this research, Integrated Water Resources Management (IWRM) methodology was applied through Watershed/Basin Simulation Models for general river basins. The model chosen and used after subjection to several criteria was DHI Model, MIKE BASIN 2009 Version. It was then appropriately developed through calibration on data from the study catchment, input data formatting and its adaptation to the catchment characteristics. The methodology involved using spatio-temporal demographic and hydrometeorological data. It was established that the model can be used to predict the impact of projects on the already existing enviro-hydrological system while assigning priority to water users and usage as would be deemed necessary, which is a significant procedure in IWRM-based environmental rehabilitation/remediation. The setback was that the available records from the various offices visited had a lot of data gaps that would affect the degree of accuracy of the output. These gaps were appropriately infilled and gave an overall output that was adequate for inferences made therefrom. Several scenarios tested included; use and abstraction for the present river situation, the effect of wet/dry seasons on the resultant water available for use, and proposed projects being constructed on and along the river. Results indicated that the river had insufficient flow to sustain both the current and proposed water users. It was concluded that irrespective of over exploitation, lack of adequate rainfall was not a reason for the low discharge but rather the loss of rainwater as evaporation, storage in swamps/wetlands, and a considerable amount of water recharging groundwater aquifers. Thus, the proposed remedy is to increase the exploitation of the groundwater resource in the area and reduce the number of direct river water users, improve farming methods and conjunctive use of groundwater and surface water - the latter as a dam on River Rwizi. The advantage of the dam is that the water usage can be controlled as necessary in contrast to unregulated direct abstraction, thus reducing the risk of subsequent over-exploitation. / Vaal University of Technology

Die genaue Kenntnis über den Wasserhaushalt stellt die Grundlage für die Bewirtschaftung der Ressource Wasser dar. Im urbanen Raum spielen dabei die siedlungshydrologischen Randbedingungen, wie Versiegelung, Anschlussgrad an die Kanalisation oder wasserbauliche Eingriffe, eine nicht zu vernachlässigende Rolle. Zur Quantifizierung der verschiedenen Wasserhaushaltsgrößen wurde ein konzeptioneller Ansatz entwickelt, der die jeweiligen Randbedingungen berücksichtigt und deren gegenseitige Beeinflussung abbildet. Hierbei muss der Einfluss auf den Wasserhaushalt auch bei veränderten Bedingungen simulierbar sein. Als Untersuchungsgebiet wurde das Gebiet der Wuhle, ein rechter Nebenfluss der Spree, gewählt, da es alle relevanten Aspekte der Wasserwirtschaft beinhaltet. Die Wuhle entspringt auf der Barnim-Grundmoränenhochfläche bei Ahrensfelde und mündet nach etwa 15,7 km Lauflänge im Stadtteil Köpenick in die Spree. Der Ansatz beruht auf der Berechnung der Wasserhaushaltsgrößen mit Hilfe eines flächendifferenzierten Verfahrens zur Ermittlung des Gesamtabflusses aus Niederschlag abzüglich der Verdunstung sowie dessen Aufteilung in einen oberirdischen und einen unterirdischen Teil. Zur Verifizierung der wasserhaushaltlich bestimmten Abflussgrößen wurden detaillierte hydraulische Untersuchungen an der Wuhle durchgeführt und abschnittsweise interpretiert. Anschließend wurde mit Hilfe der Förderdaten der Wasserwerke eine Grundwasserhaushaltsbilanz durchgeführt. Im Ergebnis ließ sich hydrogeologisch der Anteil an Uferfiltrat an der Gesamtfördermenge ermitteln. Zur Simulation des Einflusses des Wasserhaushaltes und der Grundwassernutzung auf den Grundwasserkörper wurde mit Hilfe des Simulators FEFLOW© eine numerische Modellierung der Strömungsverhältnisse durchgeführt. Über den Abgleich der simulierten Grundwasserhöhen mit den Grundwasserständen aus der Stichtagsmessung erfolgte eine zusätzliche Überprüfung der wasserhaushaltlich berechneten Abflussgrößen. / The exact knowledge of the water balance is the basis of the water supply and distribution within a catchment area. In an urban area the boundary conditions of the civil engineering like the sewer system or the hydraulic engineering plays an important role. To quantify the water balance a conceptual approach was developed which takes the current conditions and their interdependence into consideration. The impact of changing conditions on the water balance can also be simulated. As investigation area the catchment of the Wuhle River was chosen because it includes all relevant aspects of water management. The Wuhle River has its source on the ground moraine of the Barnim plateau directly at the city boundary in Ahrensfelde and reaches the Spree in the quarter Köpenick after about 15.7 km. This method uses a differentiated calculation by area to determine the total outflow of rainfall minus evaporization. It also determines the submontane and aboveground distribution. For verification purposes detailed hydraulic investigations were carried out at the Wuhle. With the production rate of the waterworks the groundwater balance was then calculated. As a result the amount of bank filtrate of the total groundwater withdrawal was determined in a hydro geological way. Using the simulation software FEFLOW© a numeric model of the flow pattern was created to simulate the influence on the water balance and the groundwater. The displayed subterranean catchment area of the water work Wuhlheide was based on the water table contours which were interpolated from a fixed date measurement of the groundwater heads. By comparing the simulated groundwater heads and the water levels from the fixed date measurement an additional verification of the water balance was realised.

In der vorliegenden Arbeit wurde untersucht, inwieweit die Reproduktionsbiologie von aquatischen Lebewesen durch die Gewässerbelastung mit endokrin wirksamen Substanzen (endocrine disruptors, ED) beeinflusst wird. Mit dem Amphib Xenopus laevis steht ein etabliertes Studienmodell zur Untersuchung der Wirkungen von ED auf die Reproduktionsbiologie zur Verfügung, das für die vorliegenden Studien modifiziert und erweitert sowie mit gewässeranalytischen Methoden verknüpft wurde. Die Gefährdung wasserlebender Tiere durch Gewässerbelastung mit ED kann erfasst werden, indem die Wirkung einer ausgewählten Einzelsubstanz auf die Reproduktionsbiologie untersucht wird. Anschließend erfolgt ein Nachweis der Substanz in Umweltproben. Durch Expositionsversuche, histologische Untersuchungen und Expressionsnachweis eines molekularen östrogenen Biomarkers konnte festgestellt werden, dass Bisphenol A (BPA) in Kaulquappen von Xenopus laevis verweiblichend wirkt und seine Effekte über eine Bindung an den Östrogenrezeptor vermittelt. Chemische Analysen während der Expositionsversuche zeigten, dass BPA von den Kaulquappen aufgenommen wird und dass eine geringe Abbaubarkeit der Substanz während eines Zeitraums von 48 Stunden besteht. Die Analyse von BPA in Wasserproben, die aus dem Fluss Alb oder aus Kläranlagenausläufen stammten, zeigte, dass BPA im Gewässer in relevanten Konzentrationen vorhanden ist und hauptsächlich durch eine Kläranlage in den Fluss eingeleitet wird. In einem Gewässer liegt allerdings ein Gemisch aus unterschiedlichen ED mit verschiedenen Wirkmechanismen vor. Die Gewässerbelastung mit endokrin wirksamen Substanzen kann weiterhin untersucht werden, indem Gewässerextrakte fraktioniert und in in vitro-Screeningmethoden getestet werden. Als Screeningmethoden dienten Rezeptorbindungsstudien an Östrogen- und Androgenrezeptoren sowie die Behandlung von Leberzellkulturen mit den Gewässerextrakten aus der Alb, um eine Regulation der Expression bestimmter Biomarkergene durch potenzielle ED nachzuweisen. Dazu wurde als neuer (anti)androgener und (anti)östrogener Biomarker das Retinol-binding Protein eingeführt. Die Untersuchung der Gewässerextrakte mit diesen Methoden zeigte, dass die Alb eine Belastung mit endokrin wirksamen Substanzen aufweist und dass hauptsächlich östrogen wirksame Substanzen vorkommen. Die Proben aus den Kläranlagenausläufen weisen die höchste endokrine Aktivität auf. / The present study examined the influence of endocrine active compounds (endocrine disruptors, ED), which are present in surface waters, on reproductive biology of aquatic organisms. The amphibian Xenopus laevis is a well-established model organism for the study of effects of ED on reproduction. It has been modified and broadened for the purpose of this study, and it was combined with chemical methods for water analyses. It is possible to assess water pollution with ED by detecting effects on repro-ductive biology of one particular substance, and then by looking for this substance in environmental water samples. We showed the feminizing potency of Bisphenol A (BPA) in conducting exposure experiments with tadpoles, in examining histological samples of gonads and in detecting the induction of the expression of a molecular estrogenic biomarker. BPA was recognized to mediate its effects via binding to the estrogen receptor. Moreover, analysis of BPA during exposure experiments revealed that BPA is taken up by tadpoles and is not readily degradable during a time period of 48 hours. Chemical analyses of environmental water samples from the river Alb or samples from sewage treatment works (STW) showed that BPA is released into the environment by STW effluents. In surface waters, there are different kinds of ED with different modes of action. Thus, it is another possibility to assess water pollution with ED by fractionating environmental water samples and by testing these fractions in rapid in vitro-screening methods. In the present work, receptor binding assays were carried out, both examining the binding to estrogen and androgen receptors. Furthermore, Xenopus laevis hepatocyte cultures were treated with fractions of environmental samples and biomarker expression was detected. A new biomarker to assess (anti)androgenic or (anti)estrogenic modes of action, respectively, was established. This new biomarker was the Retinol-binding Protein. The results obtained by these methods revealed that the river Alb is mainly polluted with estrogenic ED. Samples from STW effluents possessed the highest endocrine activity.

In dieser Dissertation wurden das Auftreten und die ökologische Bedeutung Vivianits in Süßwassersedimenten erforscht. Vivianit ist das am weitensten verbreitete reduzierte Eisenphosphatmineral, das sich in Gewässersedimenten bildet. Über die Mechanismen der Vivianitbildung in Sedimenten und die quantitative Rolle des Minerals für die Speicherung von Phosphor ist bisher wenig bekannt. Die neuen Erkenntnisse dieser Arbeit basieren auf der Entwicklung einer neuartigen Methode, die eine direkte Identifikation Vivianits mittels Röntgendiffraktometrie in Sedimenten erlaubte. Es gelang erstmalig, Vivianit in Oberflächensedimenten zu quantifizieren. Die vorliegende Arbeit zeigt, dass Vivianit signifikant, mit 10-40 %, zur Phosphorretention in Süßwassersedimenten beitragen kann. Die Untersuchung der Bildungsbedingungen Vivianits in unterschiedlichen Gewässersedimenten Norddeutschlands zeigte, dass das molare Schwefel zu Eisen Verhältnis des Sediments als ein wichtiger Indikator für die Bedingungen identifiziert, welche die Triebkräfte für die An- und Abwesenheit Vivianits darstellen. Eine Eutrophierung von Gewässern und der damit verbundene Anstieg der Sulfidproduktion kann dabei die Bildung Vivianits beeinträchtigen, und eine Abnahme des Phosphorbindungsvermögens des Sediments zur Folge haben. Die vorliegende Arbeit macht deutlich, dass eine artifizielle Erhöhung des Eisengehaltes des Sediments im Rahmen einer Seenrestaurierung eine Vivianitbildung induzieren kann und so langfristig zu einem erhöhten Phosphorrückhalt führt. Sättigungsberechnungen ergaben, dass ein hinsichtlich Vivianits übersättigtes Porenwasser kein sicheres Indiz für die Anwesenheit des Minerals ist. Die Berechnungen sind nicht in der Lage die kleinskaligen chemischen Bedingungen im Porenraum des Sediments abzubilden. Die Untersuchungen zeigen, dass die Bildung von Vivianit einen wichtigen Prozess der Phosphorbindung in Gewässersedimenten darstellt, der bislang jedoch weitestgehend vernachlässigt wurde. / In this thesis, the occurrence and environmental relevance of vivianite in freshwater sediments were explored. Vivianite is the most common reduced iron phosphate mineral which forms in sedimentary environments. Not much is known about the mechanisms which lead to vivianite formation in surface sediments, and about the quantitative role of vivianite in phosphorus sequestration. The development of a novel sediment preparation technique allowed the direct identification of vivianite by powder X-ray diffraction. Notably, for the first time, vivianite was quantified in surface freshwater sediments. The study examplifies that vivianite can significantly contribute to the phosphorus retention in surface freshwater sediments, accounting for 10-40 % of total sedimentary phosphorus. The exploration of vivianite in different surface freshwater sediments located in northern Germany revealed that the sedimentary sulphur to iron ratio is a valuable indicator for the conditions that are important drivers behind the formation or absence of vivianite. It has been demonstrated that eutrophication and the accompanied increase in sulphide production hampers vivianite formation, leading to a decreased phosphorus binding capacity of sediments through increased sediment sulphidization. The present study also revealed, that an iron addition as a measure of lake restoration can trigger vivianite formation, and significantly increases the long-term phosphorus retention of sediments. Pore water equilibrium calculations demonstrated that supersaturated pore water is not sufficient to predict the occurrence of the mineral in situ. Those calculations often fail to predict the occurrence of vivianite because they do not adequately represent chemical conditions within sediment microenvironments. In summary, the formation of vivianite in aquatic sediments constitutes an important process in phosphorus sequestration which has so far largely been ignored.

Natürliche Niederungsgebiete wirken als effektive Phosphor Senke. Landwirtschaftliche Nutzung und Drainage führt zur Transformation zu Phosphor Quellen. Dem Spreewald, ein Feuchtgebiet und seiner Funktionsweise als Phosphor Quelle oder –Senke, kommt im Einzugsgebiet der Spree eine wichtige Rolle zu. Die vorhandenen Kenntnisse der Phosphor Umsatzprozesse und des Phosphor Austausches zwischen den Flächen und dem Fließgewässernetz sind jedoch gering. Praktikable Ansätze zur Beschreibung des Phosphor Austauschverhaltens von Nährstoffen in den ausgedehnten Polderregionen liegen nicht vor. Anhand hydrologischer, geohydraulischer und biogeochemischer Prozessuntersuchungen in einer Polderlandschaft mit typischer Stauhaltung konnten die Phosphor Freisetzungs- und Retentionsprozesse ausgewiesen werden. Unter Nutzung verschiedener Modellansätze (geohydraulische Modellierung, Stofftransportmodellierung und Statistische Modelle) und der Berechnung von Phosphor Prozessraten werden horizontale und vertikale Phosphor Fluxe in den Flächen-Wasser Übergangszonen quantifiziert. Die Ergebnisse gehen in ein Phosphor Bilanzmodell ein, das die P-Quellen und Senkenfunktion von Polder Teilflächen (überstaut, genutzt) und des gesamten Polders in Monatsschritten abbildet. Die biogeochemischen Phosphor Umsatzprozesse sowie der horizontale und vertikale Transport werden wesentlich von den hydrologischen und den klimatischen Bedingungen gesteuert. Sie stellen die primären Einflussgrößen der P Senken oder -Quellenfunktion dar. Im Polder wird die Phosphor Netto Freisetzung der genutzten Bereiche durch eine hohe Phosphor Netto Retention in den überstauten Flächen abgemindert. Szenario Untersuchungen zeigen, dass sinkende Grabenwasserstände zu einer erheblichen Erhöhung der Phosphor Emissionen aus dem Grundwasserpfad führen. Ansteigende Phosphor Fluxe bei sinkenden Wasserständen legen ein zunehmendes Eutrophierungsrisiko in den Gräben sowie für unterhalb gelegene aquatische Systeme nahe. / Natural wetlands effectively retain phosphorus. Agricultural cultivation and drainage by ditches transform them to phosphorus sources. In the Spree catchment, the Spreewald, a large scaled lowland has a strategic importance operating as a phosphorus sink or phosphorus source. Anyhow, knowledge of its phosphorus turnover processes and the phosphorus exchange behavior between the plain and the river and ditch network are marginal. Practicable approaches to reproduce the phosphorus exchange behavior in its typical polder areas are missing. Based on process investigations in a polder area with typical weir regulation, phosphorus retention and remobilization processes are characterized. Combining different model approaches (groundwater modeling, matter transport modeling and statistical models) and calculating process rates, the horizontal and vertical phosphor fluxes in the water soil/sediment transition zones are quantified. The outcomes are used as input data for a phosphorus balance model reproducing the phosphorus source and sink character of used and rewetted polder areas and for the whole polder in monthly time steps. Results from process and transport investigations point out that biogeochemical turnover processes and horizontal or vertical phosphorus transport are driven by hydrological and climatological conditions. Net phosphorus release found in the extensive used polder areas is counteracted by significant net phosphorus retention in the rewetted parts. Scenario analyses identify decreasing ditch water levels to cause a considerable increase of phosphorus emissions from the groundwater pathway. Consequently, the increasing phosphorus fluxes at decreasing water levels provoke a growing risk for eutrophication in the ditches but also in the downstream aquatic systems.

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.