Durante la última década se han publicado un gran número de estudios de investigación sobre la ubicuidad de diferentes contaminantes orgánicos en todo tipo de matrices ambientales, principalmente en agua. Entre éstos, la presencia medioambiental de fármacos y en concreto de antibióticos ha sido investigada con especial interés, debido a sus altas tasas de consumo y elevada actividad biológica (promoción de resistencia bacteriana). A este deterioro de la calidad de los recursos hídricos se une además el problema de su escasez, sobre todo en las cuencas mediterráneas, de modo que la reutilización del agua se hace imprescindible. Sin embargo, la falta de eficacia de los sistemas convencionales de tratamiento de aguas residuales para eliminar estos contaminantes orgánicos pone de manifiesto su entrada continuada en las aguas superficiales receptoras mediante los efluentes de las depuradoras, y el riesgo que supondría esta reutilización. Así pues, queda patente la necesidad de disponer de información nueva y valiosa sobre la presencia medioambiental de las sulfamidas, familia de antibióticos de alto consumo y cuya presencia medioambiental tiene origen en un uso principalmente veterinario y agrícola, (sulfametazina, sulfadimetoxina), pero también humano (sulfametoxazol, sulfapiridina). Para ello, es necesario el desarrollo de diversas herramientas analíticas avanzadas que nos permitieran la determinación de esta familia de antibióticos en diferentes matrices de agua ambiental, así como en fango de depuradora y suelo agrícola. Con las diferentes metodologías analíticas se pretende evaluar la presencia y persistencia de estos antibióticos y de sus metabolitos mayoritarios en los diferentes ecosistemas acuáticos, evaluando la eficacia de las técnicas de tratamiento de aguas residuales convencionales aplicadas en la actualidad en diferentes EDARs, y también de varias alternativas como los bioreactores de membrana o los bioreactores de lecho fijo (MBR o FBBR, respectivamente). Asimismo, estudiando su biodegradabilidad y persistencia medioambiental, es posible conocer en mayor profundidad la naturaleza y comportamiento de estos compuestos. Considerando todo lo anterior, durante el desarrollo de esta Tesis nos hemos marcado como principal objetivo el desarrollo y aplicación de nuevas metodologías analíticas basadas en la cromatografía de líquidos acoplada a la espectrometría de masas para la determinación de sulfamidas y sus metabolitos acetilados en aguas (residuales, superficiales, subterráneas) y matrices sólidas (fangos de depuradora y suelos agrícolas). Durante el análisis de aguas residuales, se evaluó también la eliminación de estos compuestos durante el tratamiento en las diferentes depuradoras, comparando la eficacia de diferentes tipos de tratamiento y su impacto en las zonas de vertido, comprendiendo así el destino de estos antibióticos en todo el ciclo del agua. Posteriormente, estudiamos la biodegradabilidad de diferentes sulfamidas mediante el tratamiento con hongos en medio líquido y sólido, y se llevó a cabo la identificación de los productos de transformación derivados mediante cromatografía de líquidos de ultra-alta resolución-espectrometría de masas en tándem con un sistema híbrido cuadrupolo tiempo de vuelo (UHPLC-QqTOF-MS/MS). También realizamos un estudio de destino de las sulfamidas, evaluando la fotodegradación de algunas de ellas y sus metabolitos acetilados en diferentes matrices acuosas, considerando también la aparición e identificación de los productos de fototransformación que se generan durante su fotólisis mediante UHPLC-QqTOF-MS/MS. Por último, mencionar que con los datos de presencia medioambiental obtenidos se llevó a cabo la evaluación del impacto medioambiental de las sulfamidas detectadas en los diferentes tipos de agua estudiados, estimando los coeficientes de riesgo asociados siguiendo las directrices marcadas por la Agencia Europea del Medicamento (EMEA). / Sulfonamides (SAs) are one of the most widely used antibiotics in human and especially in animal husbandry. So far, concern regarding the environmental presence of sulfonamides and other species of antibiotics has focused mainly on the potential spread of antimicrobial resistance. However, their biological activity and high resistance to biodegradation may lead to long residence times in both water and soil matrices. Long-term ecological risks and unpredicted effects can result from unintentional exposure of different organisms and even human health could be negatively affected. In this context, this PhD thesis aimed to study the environmental occurrence of the most relevant sulfonamides in all types of waters, sewage sludge and agricultural soils. In order to fully understand the fate and effects of this family of antimicrobials in the environment, further research on their resiliance and biodegradability has been carried out. The need of developing new advanced analytical methodologies, fast, robust and with high sensitivity for the analysis of sulfonamides and their acetylated metabolites at environmental levels was the first and one of the main objectives of this PhD Thesis. These analytical methodologies were succesfully applied for the analysis of real samples in different monitoring studies in wastewater treatment plants, rivers and aquifers. Sulfonamides and their acetylated metabolites were ubiquitous in all the water samples studied, with levels ranging from the low pg L-1 to μg L-1 (mainly in wastewater influents, but also in some surface water samples from the Llobregat River). Maximum levels detected in sewage sludge were up to 139.2 ng g-1 (sulfamethazine). The last part of the PhD focused on the biodegradability and behaviour of the sulfonamides in the environment. The efficiency of conventional wastewater treatments, usually based on activated sludge (CAS), was evaluated and removal rates were estimated for the different sulfonamides studied. The ability of white rot fungi Trametes versicolor to degrade sulfamethazine was also studied, as well as the photodegration kynetics of sulfapyridine, sulfamethazine and their respective acetylated metabolites in wastewater effluents and HPLC water under simulated irradiation.

Los estudios de biomonitorización con aves rapaces permiten evaluar el grado de contaminación ambiental y las consecuencias sobre la salud humana y ambiental. Los niveles de metales e insecticidas organoclorados en sangre de pollos de Búho real del sureste de España fueron en general bajos, siendo los niveles de plomo significativamente superiores en los individuos nacidos en una antigua zona minera. La enzima δ-ALAD es un biomarcador sensible de exposición y efecto a plomo en esta especie. El estudio de organoclorados y PBDEs en huevos no eclosionados sugiere cambios en la dieta o posibles focos de contaminación en la zona. El grosor de cáscara de huevo disminuyó conforme aumentaron las concentraciones de p,p’-DDE, alcanzando un porcentaje de disminución relacionada con declives poblacionales en aves a niveles de DDE superiores a 100 ng/g de peso de lípidos. El desarrollo de una nueva técnica permitió detectar residuos de rodenticidas en el 83% de las muestras de hígado. / Biomonitoring studies with raptor birds can be used to evaluate environmental pollution and consequencies to human and environmental health. Levels of metals and insecticides in blood of eagle owl chicks from Southeastern Spain were in general low, being lead levels significantly higher in individuals born in an ancient mining area. The enzime δ-ALAD is a sensitive biomarker of exposure and effect to lead in this species. The study of organochlorine and PBDEs in unhatched eggs suggests dietary shifts or pollutant sources. Eggshell thickness decreased with increasing p,p’-DDE, reaching a level related to population declines in birds when DDE levels exceded 100 ng/g lipid weight. The development of a new tecnique permited the detection of rodenticide residues in 83% of the liver samples.

Petroleum refineries emit a variety of airborne substances which may be harmful to human health. HEIDI II (Health Effects Indicators Decision Index II) is a computer-based decision analysis tool which assesses airborne emissions from Canada's oil refineries for reduction, based on ordinal ranking of estimated health impacts. The model was designed by a project team within NERAM (Network for Environmental Risk Assessment and Management) and assembled with significant stakeholder consultation. HEIDI II is publicly available as a deterministic Excel-based tool which ranks 31 air pollutants based on predicted disease incidence or estimated DALYS (disability adjusted life years). The model includes calculations to account for average annual emissions, ambient concentrations, stack height, meteorology/dispersion, photodegradation, and the population distribution around each refinery. Different formulations of continuous dose-response functions were applied to nonthreshold-acting air toxics, threshold-acting air toxics, and nonthreshold-acting CACs (criteria air contaminants). An updated probabilistic version of HEIDI II was developed using Matlab code to account for parameter uncertainty and identify key leverage variables. Sensitivity analyses indicate that parameter uncertainty in the model variables for annual emissions and for concentration-response/toxicological slopes have the greatest leverage on predicted health impacts. Scenario analyses suggest that the geographic distribution of population density around a refinery site is an important predictor of total health impact. Several ranking metrics (predicted case incidence, simple DALY, and complex DALY) and ordinal ranking approaches (deterministic model, average from Monte Carlo simulation, test of stochastic dominance) were used to identify priority substances for reduction; the results were similar in each case. The predicted impacts of primary and secondary particulate matter (PM) consistently outweighed those of the air toxics. Nickel, PAH (polycyclic aromatic hydrocarbons), BTEX (benzene, toluene, ethylbenzene and xylene), sulphuric acid, and vanadium were consistently identified as priority air toxics at refineries where they were reported emissions. For many substances, the difference in rank order is indeterminate when parametric uncertainty and variability are considered.

North American populations of white-winged scoters (<i>Melanitta fusca deglandi</i>) have declined markedly over the past several decades. The causes for decline are uncertain, but likely involve a complexity of events occurring on wintering and breeding areas. To gain insight into potential cross-seasonal effects, I delineated Atlantic and Pacific wintering scoter populations and linked them to a shared breeding area using stable isotope analysis of carbon (δ13C) and nitrogen (δ15N) ratios in feathers. By applying this methodology to a marked breeding population at Redberry Lake, Saskatchewan, I assigned females to putative wintering areas and determined: (1) population structure; (2) the extent of winter site philopatry; and, (3) differences in vital rates and other variates in relation to winter origin. Discriminant function analysis of isotopic ratios in feather samples from known wintering locations resulted in classification probabilities of 96% (<i>n</i> = 149) for Pacific and 78% (<i>n</i> = 32) for Atlantic wintering scoters. Using this methodology, I determined that the Redberry Lake breeding population is comprised of approximately 75% Pacific and 25% Atlantic wintering birds, and its members exhibit high degrees of winter region philopatry based on the classification of successive recaptures over three field seasons. Annual variations in population structure, as well as differences in nest initiation dates and blood contaminant loads in relation to winter area suggest seasonal interactions may influence survival and reproductive success of this population. To gain insight into potential seasonal interactions, I examined nest success and female survival in relation to winter area. No significant differences in nest success in relation to winter area were found, but nests that failed before mid-incubation were not sampled. Adult female survival rate for 2000-2004 was estimated as 0.85, with no significant difference detected between wintering areas. This study demonstrated that it is important to link breeding and wintering areas to better understand the factors influencing population dynamics and to effectively address conservation issues.

Emerging contaminants are defined as synthetic or naturally occurring chemicals or microorganisms that are not currently regulated but have the potential to enter the environment and cause adverse ecological and/or human health effects. With recent development in analytical techniques, emerging contaminants have been detected in wastewater, source water, and finished drinking water. These environmental occurrence data have raised public concern about the fate and ecological impacts of such compounds. Concerns regarding emerging contaminants and the many chemicals that are in use or production necessitate a task to assess their potential health effects and removal efficiency during water treatment. Advanced oxidation processes (AOPs) are attractive and promising technologies for emerging contaminant control due to its capability of mineralizing organic compound via reactions with highly active hydroxyl radicals. However, the nonselective reactivity of hydroxyl radicals and the radical chain reactions make AOPs mechanistically complex processes. In addition, the diversity and complexity of the structure of a large number of emerging contaminants make it difficult and expensive to study the degradation pathways of each contaminant and the fate of the intermediates and byproducts. The intermediates and byproducts that are produced may pose potential effects to human and aquatic ecosystems. Consequently, there is a need to develop first-principle based mechanistic models that can enumerate reaction pathway, calculate concentrations of the byproducts, and estimate their human effects for both water treatment and reuse practices. This dissertation develops methods to predict reaction rate constants for elementary reactions that are identified by a previously developed computer-based reaction pathway generator. Many intermediates and byproducts that are experimentally identified for HO* induced reactions with emerging contaminants include common lower molecular weight organic compounds on the basis of several carbons. These lower carbon intermediates and byproducts also react with HO* at relatively smaller reaction rate constants (i.e., k < 109 M-1s-1) and may significantly affect overall performance of AOPs. In addition, the structures of emerging contaminants with various functional groups are too complicated to model. As a consequence, the rate constant predictors are established based on the conventional organic compounds as an initial approch. A group contribution method (GCM) predicts the aqueous phase hydroxyl radical reaction rate constants for compounds with a wide range of functional groups. The GCM is a first comprehensive tool to predict aqueous phase hydroxyl radical reaction rate constants for reactions that include hydrogen-atom abstraction from a C-H bond and/or a O-H bond by hydroxyl radical, hydroxyl radical addition to a C=C unsaturated bond in alkenes and aromatic compounds, and hydroxyl radical interaction with sulfur-, nitrogen-, or phosphorus-atom-containing compounds. The GCM shows predictability; factor of difference of 2 from literature-reported experimental values. The GCM successfully predicts the hydroxyl radical reaction rate constants for a limited number of emerging contaminants. Linear free energy relationships (LFERs) bridge a kinetic property with a thermochemical property. The LFERs is a new proof-of-concept approach for Ab initio reaction rate constants predictors. The kinetic property represents literature-reported and our experimentally obtained hydroxyl radical reaction rate constants for neutral and ionized compounds. The thermochemical property represents quantum mechanically calculated aqueous phase free energy of activation. Various Ab initio quantum mechanical methods and solvation models are explored to calculate the aqueous phase free energy of activation of reactantas and transition states. The quantum mechanically calculcated aqueous phase free energies of activation are within the acceptable range when compared to those that are obtained from the experiments. These approaches may be applied to other reaction mechanisms to establish a library of rate constant predictions for the mechanistic modeling of AOPs. The predicted kinetic information enables one to identify important pathways of AOP mechanisms that are initiated by hydroxyl radical, and can be used to calculate concentration profiles of parent compounds, intermediates and byproducts. The mechanistic model guides the design of experiments that are used to examine the reaction mechanisms of important intermediates and byproducts and the application of AOPs to real fields.

Die bisherigen Untersuchungen zu den Folgen extremer Hochwasserereignisse beschäftigten sich überwiegend mit den durch hohe Wasserstände und Fließgeschwindigkeiten verursachten direkten und tangiblen Schäden an Gebäuden und Infrastrukturen. Den durch schadstoffhaltiges Hochwasser hervorgerufenen direkten und indirekten sowie in der Regel intangiblen Konsequenzen für Mensch und Umwelt ist - insbesondere im Hinblick auf deren räumliche Verteilung - im Rahmen des Hochwasserrisikomanagements nur geringe Aufmerksamkeit gewidmet worden. Während Hochwasserereignissen können toxische Stoffe - wie beispielsweise Arsen, Blei, Cadmium oder Quecksilber sowie persistente organische Kontaminanten wie DDT oder HCH - aus belasteten Gewässer- und Ufersedimenten sowie Altstandorten und Altablagerungen freigesetzt werden. Diese Stoffe werden von der Hochwasserwelle aufgenommen, zum überwiegenden Teil partikulär gebunden transportiert und bei nachlassender Fließgeschwindigkeit und ablaufendem Hochwasser als Sedimente in den Überflutungsbereichen deponiert. In Abhängigkeit von der Nutzung der überschwemmten Gebiete sind nach einem Hochwasser unterschiedliche Rezeptoren den abgelagerten Sedimenten und darin enthaltenen Schadstoffen in der Regel langfristig ausgesetzt. Mögliche Rezeptoren sind zum Beispiel Menschen, Nutz- und Wildtiere, Futter- und Nahrungspflanzen sowie Böden mit ihren spezifischen Bodenfunktionen. Kern dieser Arbeit ist die Entwicklung einer räumlich differenzierten Methodik zur integrierten Analyse und Bewertung von stofflichen Hochwasserrisiken. Um deren Anwendbarkeit zu überprüfen, wird die entwickelte Methodik im Rahmen einer Fallstudie an Überflutungsbereichen entlang des Unterlaufes der Vereinigten Mulde zwischen Bitterfeld und Priorau erprobt, wobei der Fokus auf dem Rezeptor Mensch liegt. Die Methodik basiert auf der Integration von Verfahren der Hochwasserrisikoanalyse und der Schadstoffrisikoanalyse. Diese werden unter Verwendung eines angepassten Source-Pathway-Receptor-Consequence-Konzeptes kombiniert. Die Methodik besteht aus drei größeren Hauptelementen: (1.) der Gefahrenanalyse, (2.) der Expositionsanalyse und (3.) der Schadstoffrisikocharakterisierung und -bewertung. Die Gefahrenanalyse beschreibt die Freisetzung, den Transport und die Ablagerung der Stoffe in Abhängigkeit von der Hochwassercharakteristik, den Substanzeigenschaften sowie den Verteilungsprozessen nach der Ablagerung, beispielsweise dem Transfer vom Boden in die Pflanze. Ergebnisse der Gefahrenanalyse sind Karten der Schadstoffquellen in Form räumlich verteilter Stoffkonzentrationen in Umweltmedien wie Böden und Pflanzen. Die Expositionsanalyse stellt die Verbindung zwischen den Schadstoffquellen und den Rezeptoren her. Bindeglied sind Expositionspfade, beispielsweise die orale Aufnahme von kontaminiertem Boden oder der Verzehr von Pflanzen, die auf belasteten Böden angebaut werden. Teil der Expositionsanalyse ist eine so genannte Rezeptoranalyse, die - aus Landnutzungstypen abgeleitet - Vorkommen bestimmter Rezeptoren identifiziert und diese charakterisiert. Dabei bezieht die Rezeptoranalyse sowohl die räumliche Verteilung der Rezeptoren als auch deren Eigenschaften ein. Für den Rezeptor Mensch sind dies etwa physiologische Parameter wie Körpergewicht oder Atemrate sowie verhaltensbezogene Parameter wie Zeit-Aktivitätsbudgets oder Nahrungsaufnahmeraten. Daran anschließend wird mit der Expositionsanalyse im engeren Sinne die Exposition der Rezeptoren gegenüber bestimmten Stoffen quantifiziert, indem Transfer- und Aufnahmeraten von Expositionsmedien wie Boden, Nahrung oder Luft ermittelt und mit den darin enthaltenen Stoffkonzentrationen in Beziehung gesetzt werden. Ergebnis der Expositionsanalyse sind räumlich explizite Darstellungen der inneren Exposition, d.h. täglich aufgenommener resorbierter Schadstoffmengen. Darauf folgend werden im Zuge der Risikocharakterisierung die Effekte der Exposition mit Hilfe von Dosis-Wirkungsbeziehungen analysiert, die dann in Form von toxikologisch begründeten Referenzwerten als Basis für die finale stoffbezogene Risikobewertung dienen. Diese erfolgt durch Vergleich der inneren Exposition mit toxikologischen Referenzwerten in Form von tolerablen Aufnahmeraten. Die gesundheitlichen Risiken werden durch den Quotienten aus resorbierter Dosis und tolerabler Dosis beschrieben und als stoff- und pfadspezifischer Risikoindex flächenhaft dargestellt. Abschließend erfolgt eine Bewertung der Risiken mittels einer die Unsicherheiten der Referenzwerte berücksichtigenden Bewertungsfunktion. Die Methodik ist in Form eines GIS-basierten Rechenmodells umgesetzt und im Rahmen einer Fallstudie an der Vereinigten Mulde für verschiedene hydraulische Szenarien im Sinne simulierter Abflüsse verschiedener Jährlichkeiten - 100, 200 und 500 Jahre - erprobt worden. Als ausgewählte Ergebnisse liegen räumlich differenzierte Risikobewertungen für die Stoffe Arsen, Cadmium, Quecksilber und Blei unterschieden nach den Expositionsmedien Boden/Hausstaub, Luft sowie pflanzliche Nahrung vor. Exemplarisch seien hier ausgewählte Bewertungsergebnisse in Form des sogenannten Gefahrenwertes für ein HQ500-Szenario dargestellt: Durch die orale Aufnahme von Arsen über Boden/Hausstaub wird für den Rezeptor Kleinkinder räumlich begrenzt die Risikoschwelle überschritten, wobei die Handlungsschwelle nicht erreicht wird. Die Ergebnisse für Cadmium, Quecksilber und Blei liegen deutlich unter der Risikoschwelle. Ein ähnliches Bild zeigt sich für die Aufnahme über die Luft. Hier wird bei lebenslanger Exposition für Arsen die Risikoschwelle überschritten, für die anderen Stoffe werden Gefahrenwerte weit unter der Risikoschwelle ermittelt. Bezogen auf den Verzehr von Nahrungspflanzen aus Eigenanbau zeigen sich bei lebenslanger Exposition für Cadmium großräumig erhebliche Überschreitungen des Handlungsschwellenwertes. Für die anderen Stoffe finden sich nahezu flächendeckend Überschreitungen des Risikoschwellenwertes, die aber nicht an die Maßnahmenschwelle heranreichen. / Research on the consequences of flood events has so far focused on direct tangible damages to buildings and infrastructure caused by high water levels and flow velocities. In the context of flood risk management only little interest has been paid to direct and indirect as well as dominantly intangible consequences caused by flood pollutants to human and ecological receptors - especially taking their spatial distribution into account. During floods toxic substances such as trace elements (e.g. Arsenium, Cadmium, Mercury, Lead, Zinc) and persistent organic pollutants (e.g. HCHs, DDX) can be released from contaminated river bank sediments or former industrial sites. These substances are taken up by the flood water, get transported - mainly bound to fine particles - and get deposited as sediments in the floodplain in case of decreasing flow velocities. Depending on the land use in the floodplain, different receptors can be exposed to the sediments with the associated contaminants. Potential receptors are humans, livestock, wild animals, food and fodder plants as well as soils with their specific soil functions. The core of this thesis is the development of a spatially explicit methodology which enables the integrated analysis and evaluation of substance-based flood risks. To test the applicability, the developed methodology is applied within a case study dealing with floodplains along the lower reaches of the Vereinigte Mulde River situated between Bitterfeld and Priorau (Saxony-Anhalt, Germany). In this case study, the focus is on the receptor man or, more specifically, human health. The methodology is based on an integration of procedures from the fields of flood risk analysis and contaminant risk analysis. These procedures are integrated using an adopted Source-Pathway-Receptor-Consequence concept. The three main elements of the methodology are hazard analysis, exposure analysis and contaminant risk determination and evaluation. At first, the hazard analysis describes the release, transport and deposition of substances based on flood characteristics and substance properties as well as fate and transfer processes after sedimentation (e.g. soil-to-plant transfer). Results of the hazard analysis are maps of spatially distributed substance concentrations in environmental media such as soils and plants, i.e. the (secondary) contaminant sources. Within the exposure analysis the linkages between the contaminant sources and the receptors are described. Connecting elements are exposure pathways such as the ingestion of contaminated soil or the consumption of food produced on such soils. Part of the exposure analysis is a so-called receptor analysis which indicates and characterises potential human receptors that are derived from land-use types. The receptor analysis takes the receptors\' spatial distribution as well as certain properties into account. Taking the receptor human, these properties are physiological parameters such as body weight or respiration rate and behavioural parameters, e.g. activity budgets or food consumption patterns. Subsequently, with the exposure analysis in a narrower sense, the exposure of the receptors to a certain substance is quantified by calculating transfer and intake rates of exposure media such as soil, food or air taking into account the corresponding substance concentrations in these media. Results of the exposure analysis are spatially explicit representations of absorbed contaminant amounts for a certain receptor, i.e. daily resorbed exposure doses. In the course of the contaminant risk determination, the effects (consequences) of the receptors\' exposure are analysed by dose-response relationships, setting the basis for the final substance-based risk assessment in terms of toxicologically derived reference values. Health risks are expressed as ratio between calculated resorbed dose and tolerable resorbed dose and are presented as maps of substance- and pathway-specific risk indices. In a final step, an evaluation is carried out based on a method that takes the uncertainty of the toxicological reference values into account. The methodology has been implemented in a GIS-based calculation model and was applied within a case study to simulate floods with certain return periods (100, 200, and 500 years). Selected results are spatially differentiated risk evaluations for the substances arsenic, cadmium, mercury and lead distinguished based on the exposure media soil/house dust, air and home-grown vegetable food. Taking the 500-year flood-scenario and the risk evaluation value as an example, the following results have been derived: the oral intake of arsenic via soil/house dust leads to a spatially restricted exceedance of the risk level of the receptor infant, whereas the action level is not reached. The results of cadmium, mercury and lead are clearly below the risk level. A similiar pattern shows for the pulmonary intake via air. Based on lifetime exposure, the risk level for arsenic is exceeded, for all other substances the values are far below the risk level. Considering the intake of cadmium via consumption of home-grown vegetables, the action level is notably exceeded in large areas. The other substances show a nearly general exceedance of the risk level without reaching the action level.

Atualmente no cenário mundial a qualidade da água tem gerado muitas preocupações, pois milhares de produtos sintéticos são produzidos para facilitar muitas práticas industriais, domésticas e pessoais e com isso diversas substâncias químicas utilizadas para esses fins são introduzidas no meio ambiente. Os parabenos são substâncias químicas utilizadas pelas indústrias farmacêuticas, de alimentos e cosméticos e que cuja função é a conservação, sendo que há muitos questionamentos em relação a sua segurança, pois alguns relatórios têm mostrado que a exposição a esses parabenos pode modular ou perturbar o sistema endócrino e com isso gerar consequências prejudiciais à saúde humana e aos ambientes aquáticos. Esse estudo teve como objetivo avaliar a presença dos Parabenos Metilparabeno e Propilparabeno no ambiente aquático e os seus potenciais estrogênicos e a toxicidade aguda. A metodologia se desenvolveu a partir do ensaio in vitro YES para a determinação da atividade estrogênica, ensaios de toxicidade aguda em Daphnia similis e em Aliivibrio fischeri e a quantificação dos parabenos na água do Rio Maracanã-RJ através da cromatografia líquida acoplada ao espectrômetro de massa. Os resultados obtidos para a CE50 dos MP e PP, a partir do ensaio in vitro YES, foi de 18,91 mgL-1 e 7 mgL-1 e a magnitude da resposta foi de 10-5 e 10-4 menos potente que 17ß-estradiol para o MP e o PP, respectivamente. A partir do ensaio de toxicidade aguda, os valores de CE50 obtidos em Daphnia similis, foi de 29,42 mgL-1 e 9,94 mgL-1e em Aliivibrio fischeri foi de 3,047 mgL-1 e 1,946 mgL-1, respectivamente, com isso observou-se que o PP é mais tóxicos em todos os organismos testados, sendo mais tóxicos para um e menos para outros. A água do Rio Maracanã não foi tóxica para a Daphnia similis em nenhum dos dois pontos, já para o Aliivibrio fischeri foi tóxica em apenas um ponto. As concentrações encontradas de MP e PP foram maiores no ponto onde, de acordo com os parâmetros físico-químicos, a qualidade da água não está dentro dos padrões exigidos pela legislação, sendo quantificados na ordem de ngL-1, contudo é válido ressaltar que os DEs não são encontrados no meio ambiente separados, eles interagem entre si e provocam efeitos aditivos ou sinérgicos, sendo muito difícil de prever qual o efeito, por isso é importante o conhecimento do potencial estrogênico das substâncias simples, pois em um estudo com uma matriz ambiental, pode-se observar se houve algum efeito aditivo ou sinérgico de outras substâncias. / Currently on the world stage water quality has generated many concerns, because thousands of synthetic products are produced to facilitate many industrial, domestic and personal practices and thereby various chemicals used for these purposes are introduced into the environment. Parabens are chemicals used by the pharmaceutical, food and cosmetic and whose function is to conserve, and there are many questions regarding its safety , as some reports have shown that exposure to these parabens can modulate or disrupt endocrine system and thereby generate harmful consequences for human health and aquatic environments . The aim of this study was to evaluate the presence of Methylparaben and Propylparaben in the aquatic environment and their potential estrogenic and acute toxicity. The methodology developed from the in vitro YES assay for the determination of estrogenic activity, acute toxicity tests with Daphnia similis and Aliivibrio fischeri and quantification of parabens in water of Maracanã River RJ by liquid chromatography coupled with mass spectrometry. The EC50 results for the PP and MP, from the in vitro YES, was 18,91 mgL -1 and 7 mgL-1 and the magnitude of response was less potent 10-5 and 10-4 that 17ß - estradiol for MP and PP , respectively. From the acute toxicity test, the EC50 values obtained in Daphnia similis was 29,42 mgL-1 and 9,94 mgL-1, and Aliivibrio fischeri was 3,047 mgL-1 and 1,946 mgL-1, respectively, with it was observed that PP is more toxic in all organisms tested, and more toxic to one and less to others . The water of the Maracanã River was not toxic to Daphnia similis in either points, since for Aliivibrio fischeri was toxic at only one point. Found concentrations of MP and PP were higher at the point where, according to the physico-chemical parameters, water quality is not within the standards required by legislation and quantified in order ngL-1, however its worth to note that the DEs are not found in the middle separate environment, they interact with each other and cause additive or synergistic effects , its very difficult to predict what effect , so its important to know the estrogenic potential of simple substances , since in a study with an environmental matrix, one can observe if there were any additive or synergistic effect of other substances .

Submitted by Emanuel Varela Cardoso (emanuel.varela@ufcg.edu.br) on 2018-08-16T16:52:01Z No. of bitstreams: 1 ADRIANA VALÉRIA ARRUDA GUIMARÃES – TESE (PPGEQ) 2017.pdf: 2201140 bytes, checksum: 097db96ed09bdde84b6831586b738b25 (MD5) / Made available in DSpace on 2018-08-16T16:52:01Z (GMT). No. of bitstreams: 1 ADRIANA VALÉRIA ARRUDA GUIMARÃES – TESE (PPGEQ) 2017.pdf: 2201140 bytes, checksum: 097db96ed09bdde84b6831586b738b25 (MD5) Previous issue date: 2017-02-24 / Capes / O lodo de curtume é classificado como sendo resíduo sólido perigoso - Classe I. Desse modo, compromete o meio ambiente em virtude da presença de cromo (Cr3+), sulfetos (S2-) e elevada matéria orgânica. Nesta pesquisa, o lodo de curtume foi submetido ao processo de estabilização por solidificação, tendo como objetivos determinar a velocidade de decaimento cinético dos contaminantes além de otimizar o processo de estabilização por solidificação do lodo de curtume. O planejamento experimental realizado foi o fatorial ao acaso, com dois fatores e duas repetições, resultando em 18 tratamentos os quais utilizaram como fatores porcentagem de lodo de curtume (5%, 15% e 25%) e tempo de cura (7, 28 e 90 dias). Foi realizada a avaliação do material estabilizado por solidificação com os critérios de integridade/durabilidade e imobilização dos contaminantes. A Análise de Variância possibilitou obter a otimização do processo de tratamento do lodo de curtume, o balanço de massa e a eficiência de retenção dos contaminantes do material estabilizado. Finalmente, foi realizada a cinética dos contaminantes levando em consideração o tempo de cura e a porcentagem. O presente trabalho de tese expõe três importantes contribuições cientificas que o diferencia das demais pesquisas desenvolvidas tratando lodo de curtume. A primeira está voltada à otimização do processo de estabilização por solidificação, no qual foi encontrado o ponto ótimo entre o tempo de cura e a porcentagem de lodo de curtume. A segunda encontra-se relacionado à velocidade de decaimento cinético dos contaminantes. E finalmente, a terceira está relacionada ao balanço de massa e a eficiência do processo de E/S dos contaminantes presentes no lodo de curtume. Como resultado desse estudo verificou-se que, a otimização das respostas foi a maneira de minimizar e/ou maximizar as variáveis respostas do processo de E/S, conseguido com menor tempo de cura e menor porcentagem de lodo. De acordo com a função desejável todos os tratamentos foram aprovados nos ensaios de integridade/durabilidade e imobilização dos contaminantes, fazendo a conversão da Classe I (perigoso) para Classe II (não perigoso). Os parâmetros relacionados à integridade durabilidade obtiveram sua otimização com pontos ótimos distintos. As melhores respostas para os parâmetros ambientais nos extratos lixiviado e solubilizado foram atribuídos aos tratamentos combinados com o menor tempo de cura e a menor porcentagem de lodo de curtume. A pesquisa permitiu concluir que foi possível determinar a cinética dos contaminantes do lodo de curtume quanto à otimização do processo de E/S. Com isso, a redução na velocidade de decaimento cinético dos contaminantes ambientais, nos extratos lixiviado e solubilizado, foi atribuída aos tratamentos combinados com a menor porcentagem de lodo de curtume e tempo de cura variado. O processo de estabilização por solidificação tratando o lodo de curtume foi eficiente, uma vez que promoveu atenuação dos contaminantes convertendo da classe perigosa para não perigosa. / The tannery sludge is classified as a Class I – hazardous solid residue. It compromises the environment due to the presence of chromium (Cr3+), sulfides (S2-) and high amounts of organic matter. In this research, the tanning sludge was subjected to a solidification stabilization process, aiming to determine the kinetic decay rate of the contaminants and to optimize the stabilization process by solidification of the tannery sludge. The experimental design comprised two factors and two replicates, resulting in 18 treatments, which used percentage of tannery sludge (5%, 15% and 25%) and curing time (7, 28 and 90 days) as variables. An evaluation of the material stabilized by solidification was carried out with the criteria of integrity/durability and immobilization of contaminants. The variance analysis allowed us to obtain a process optimization of the tannery sludge treatment, the mass balance and a retention efficiency of the stabilized material contaminants. Finally, the contaminants kinetics were analyzed taking into account the tannering time and percentage. The present work is different from previous ones because it presents three important scientific contributions regarding the tannery sludge treatment. The first one is focused on the optimization of the solidification stabilization process, in which was found an ideal balance between tannering time and percentage. The second is related to the rate of the contaminants kinetic decay. The third one is related to the mass balance and an edition of the S/S process of the contaminants present within the tanning sludge. As a result of the study it was found that, an optimization of the responses to minimize and/or maximize as variables of the S/S process responses, achieved with shorter cure duration and lower sludge percentage. According to a desirable function all the treatments were approved in the integrity/durability tests and immobilization of the contaminants, converting it from a Class I (dangerous) to a Class II (non-hazardous) residue. The parameters related to the durability and integrity obtained their optimization with different optimum points. The best responses to the environmental control in the leached and solubilized extracts were attributed to the combined treatments with the lowest tannering rate and percentage of tannery sludge. The research concluded that it was possible to determine the kinetics of tannery sludge contaminants in the optimization of the S/S process. Thus, a reduction in the kinetic detoxification rate of the environmental contaminants in the leached and solubilized extracts was attributed to treatments combined with a smaller percentage of tannery sludge and varied tannering time. The solidification stabilization process used to treat the tannery sludge was efficient as it promoted the attenuation of contaminants converting it from a hazardous to a non-hazardous residue.

Emerging organic contaminants (EOCs) have been the focus of global environmental research for over three decades. EOCs have caused widespread concern due to their extensive use. As EOCs were designed to correct, enhance or protect a specific physiological, their target effects in humans and/or farm stocks are relatively well known and documented. However, there is limited knowledge about their unintended effects in the environment. To address the occurrence, distribution and fate of EOCs in the environment, efficient and reliable analytical methods are needed. The relatively low concentration, high polarity, and thermal lability of some EOCs, together with their interaction with complex environmental matrices, make their analysis challenging. Sample preparation followed by GC or HPLC separation and mass spectrometry (MS) detection has become the standard approach for evaluating EOCs in environmental samples. Physicochemical properties of EOCs range from highly water-soluble (hydrophylic) to highly water-insoluble (hydrophobic). Two groups of these EOCs were considered for study in this work. Pharmaceutical and personal care products (PPCPs) were comprehensively studied in five wastewater treatment plants and their receiving watersheds in Amathole districts in Eastern C ape, South Africa. PPCPs have been widely reported in wastewater influents, effluents, receiving rivers and biosolids, but reports of their occurrence in all these matrixes have been limited by the difficulty of analysis. Therefore, a comprehensive validation of methods was carried out on the influents, effluents, sludge and soil from the irrigated golf course where the effluent of one of the study sites was being used for over three decades now for irrigation. In all, thirteen PPCPs from five therapeutic groups were selected for study in this work because of their administering rate and availability of analytical instrument. Good limit of detection (LOD) and limit of quantification (LOQ) were achieved for the method used. The LOD for the aqueous Three different technologies were employed for the treatment of wastewater in the five selected wastewater treatment plants (WWTPs) and study was carried out to evaluate their ability to eliminate the selected compounds from the influents to the effluents using statistical analysis (ANOVA) at p<0.05 on the percentage removal rate across the three plants. The results had shown eight of the compounds having no significant difference among the treatment operations, whereas the remaining five compounds varied significantly among the treatment technologies under investigation. Principal component analysis was performed on the concentration of PPCPs, their removal rate and also on the physicochemical and treatment operation parameters. Hydraulic retention time (HRT) had correlation coefficient, r = 0.90 with the concentration of PPCPs and removal rates. Furthermore, occurrences, seasonal variation, mean concentration distribution pattern of the compounds, and temporal evaluation of the mean concentration of the pharmaceutical compounds in the five WWTPs during one year of sampling were considered. The results revealed that five products which were diclofenac, ibuprofen, paracetamol, triclosan and diethyl toluamide (DDET) were predominant among the PPCPs in all the WWTPs. The removal efficiency was highest in caffeine with 96 percent, and the lowest was obtained with carbamazepine (4 percent). Risk quotient of the concentration of PPCPs in the effluents and receiving waters was determined to assess their chronic toxicity at three trophic levels: fish, algae and matrixes studied ranged from 0.01 μg/L to 0.25 μg/L, and the LOQ from 0.02 μg/L to 0.78 μg/L. In the solid matrixes, LOD varied from 0.01 ng/g to 0.65 ng/g, and the LOQ between 0.08 ng/g and 5.17 ng/g. Better recovery efficiency was obtained with this mixture of solvents, acetone: dichloromethane (1:1), for the recovery of the five therapeutic groups in the solid matrixes using ultrasonication- assisted techniques. The results show percentage recovery values ranging from 68.8 percent to 107.5 percent diaphian. According to the environmental risk assessment results, ibuprofen and triclosan were found to be the most critical compounds due to their high risk quotient values. These findings will, therefore, help in the future evaluation of the efficiency of different treatment technologies in the removal of various PPCPs from the wastewater and their sustainable management in the aquatic resources in Eastern Cape, South Africa. For the lipophilic organochlorine pesticides (OCPs), the limits of detection (LODs) of the tested congeners varied from 0.04 ng/g (α-BHC) to 0.49 ng/g (endosulfan sulfate) and the limits of quantification ranging from 0.22 ng/g (aldrin) to 2.17 ng/g (δ-BHC).

This study aimed to evaluate commercial biofertiliser quality and awareness amongst smallholder farmers in Gauteng Province, South Africa. Sixty-seven smallholder farmers were interviewed in Gauteng Province by using a survey method, while the physicochemical and microbiological properties of 13 biofertilisers were evaluated using laboratory experiments. The results showed that awareness and use of biofertiliser are very poor, with 96% of the smallholder farmers surveyed not having biofertiliser knowledge. Furthermore, the products lack basic quality parameters: 54% contained no biofertiliser strain while all the products contained microbial contaminants. The pH, moisture content and viable microbial densities were below the acceptable standards for some of the products. Two fungal and 58 bacterial operational taxonomic units were obtained from the 16S rRNA Sanger sequences while 5 791 OTUs were obtained from the Illumina Miseq system. Approximately 40%, 41% and 59% of the isolates were positive for nitrogen-fixation, siderophore production and phosphorous solubilisation. Overall, there is a need to improve awareness amongst farmers and promote good-quality biofertiliser products for increased crop productivity. / Environmental Sciences / M. Sc. (Environmental Science)