Le milieu aquatique est le réceptacle ultime de la pollution environnementale. De nombreux micropolluants y sont présents et montrent des effets toxiques envers les systèmes aquatiques. La Directive Cadre Eau (DCE) a comme objectif la restauration du bon état écologique et chimique des milieux aquatiques d’ici 2015. Pour cela, elle impose des Normes de Qualités Environnementales (NQE) faibles et une surveillance accrue des masses d’eau. Au-delà des micropolluants réglementés, certains dits « émergents » ont été détectés à de faibles concentrations (ng.L-1) dans les systèmes aquatiques. Sous ce terme, sont regroupés les composés pharmaceutiques, certains pesticides, les hormones, etc. L’ensemble de ces micropolluants sont introduits dans l’environnement par plusieurs sources : dépôts atmosphériques, lessivage des sols, lixiviation et rejets industriels et/ou domestiques. Ces travaux de thèse ont porté plus précisément sur les alkylphénols, présents sur la liste des contaminants prioritaires dangereux de la DCE, leurs dérivés éthoxylés, le bisphénol A et les composés pharmaceutiques. Dans un premier temps, une attention particulière a été portée à l’analyse de ces composés. Les méthodes analytiques de chromatographie liquide couplée à la spectrométrie de masse simple (LC-MS) et en tandem (LC-MS/MS) pour les alkylphénols ont été optimisées en améliorant les contrôles qualités et en portant une attention particulière à l’extraction des composés sensibles aux contaminations extérieures (manipulateur, ambiance, etc.). Pour pallier aux problèmes liés à la contamination des échantillons par ces composés lors de l’extraction, la microextraction sur phase solide (SPME) et une méthode d’analyse par chromatographie en phase gazeuse couplée à la spectrométrie de masse simple (GC-MS) ont été dévelopées. Dans un second temps, le devenir et le comportement des alkylphénols, de leurs dérivés éthoxylés et des composés pharmaceutiques dans les stations d’épuration (STEP), sources d’introduction dans les systèmes aquatiques avérées, ont été étudiés. Cette étude a permis de mettre en évidence que les concentrations diminuent au cours des traitements dans les STEP pour tous les composés étudiés sauf pour l’acide alkylphénoxy acétique (NP1EC) qui est formé au cours des traitements secondaires ; la carbamazépine et dans une moindre mesure le diclofénac restent stables. Seuls les traitements tertiaires permettent une élimination significative de ces composés. La présence à plus de 50% des alkylphénols et de leurs dérivés éthoxylés dans la phase particulaire entraînent une adsorption non négligeable de ces composés dans les boues. Dans le but d’améliorer le suivi environnemental, les POCISTM standard (« Polar Organic chemical Integrative SamplersTM ») de configuration « pharmaceutiques » ont été développés lors d’expérimentations menées en laboratoire pour l’échantillonnage des alkylphénols, de leurs dérivés éthoxylés, du bisphénol A et des composés pharmaceutiques. Les alkylphénols et leurs dérivés éthoxylés sont accumulés avec un temps de latence dans les POCISTM standard montrant l’influence de la membrane sur le transfert de masse de ces composés. Les POCISTM standards ont été optimisés en changeant la nature des membranes pour l’échantillonnage des alkylphénols et de leurs dérivés éthoxylés. Ces nouveaux outils sont nommés POCISTM-like. Les POCISTM-Nylon 0,1 µm et 30 µm sont les POCISTM-like montrant un fort pouvoir concentrateur des alkylphénols, de leurs dérivés éthoxylés et du Bisphénol A tout en éliminant le temps de latence observé dans leur accumulation dans les POCISTM standards. Ces POCISTM-like ont par la suite été validés en mésocosmes puis dans le milieu naturel afin de mettre en évidence leur caractère intégratif, permettant ainsi de s’affranchir de l’effet matriciel et de détecter certains composés à des concentrations inférieures aux limites de quantification. / The aquatic environment is the ultimate receptacle of environmental pollution. Many micro-pollutants are present and show toxic effects to aquatic systems (bioaccumulation in tissues, inhibition of growth, endocrine dysfunction, etc.). The Water Framework Directive (WFD) aims to restore the good ecological and chemical quality of aquatic environments by 2015. For this, it imposes low Environmental quality standards (EQS) and increased monitoring of water bodies. Beyond regulated micro-pollutants, some "emerging" have been detected at low concentrations (ng L-1) in aquatic systems. Under this term are grouped pharmaceutical compounds, some pesticides, hormones, etc. All of these micro-pollutants are introduced into the environment through several sources: atmospheric deposition, soil leaching and industrial or domestic discharges.This work is specifically focused on alkylphenols, present on the list of priority hazardous compounds in the WFD, their ethoxylated derivatives, bisphenol A and pharmaceutical compounds. As a first step, particular attention was paid to the analysis of these compounds. Analytical methods of liquid chromatography coupled to mass spectrometry (LC / MS) and tandem mass spectrometry (LC-MS/MS) for alkylphenols were optimized by improving quality controls and paying attention to the extraction of sensitive compounds toward contamination (manipulator, atmosphere, etc.). To overcome the problems associated with sample contamination by these compounds during the extraction, solid phase microextraction (SPME) and a method of analysis by gas chromatography coupled to mass spectrometry (GC-MS) was developed. In a second step, the fate and behavior of alkylphenols, their ethoxylated derivatives and pharmaceutical compounds in sewage treatment plants (WWTPs), sources of introduction into aquatic systems proved, were studied. This study has allowed showing the decrease of concentrations during treatment in WWTPs for all compounds studied except for alkylphenoxy acetic acid (NP1EC) which is formed during secondary treatment, carbamazepine, and to a lesser extent diclofenac remain stable. Only tertiary treatments allow significant removal of these compounds. The presence of more than 50% of alkylphenols and ethoxylated derivatives in the particulate phase lead to significant adsorption of these compounds into sludges. In order to improve environmental monitoring, during experiments conducted in the laboratory POCISTM standard (Polar Organic Chemical Integrative Samplers), "pharmaceuticals" configuration, have been developed for sampling alkylphenols, their ethoxylated derivates, bisphenol A and pharmaceutical compounds. Alkylphenols and their ethoxylated derivatives are accumulated with a lag phase in standard POCISTM showing the influence of the membrane on the mass transfer of these compounds. The standard POCISTM were optimized by changing the nature of the membranes for sampling alkylphenols and their ethoxylated derivatives. These new tools are named POCISTM-like. The POCISTM-Nylon 0.1 µm and 30 µm are POCISTM-like showing a strong power concentrator for alkylphénols, their ethoxylated derivatives and BPA while eliminating the lag phase observed in standard POCISTM. These POCISTM-like were subsequently validated in mesocosms and in the environment in order to highlight their integrative nature, allowing to overcome the matrix effect and to detect some compounds at concentrations below the limits of quantification.

O fósforo é apontado como o principal responsável pelo enriquecimento nutricional de mananciais de abastecimento público, desencadeando por meio do fenômeno de eutrofização, a floração de grupos algais tóxicos e, portanto a sua remoção passa a ter grande significado para a saúde pública e para o meio ambiente. O presente trabalho foi desenvolvido com os objetivos de: avaliar a eficiência de remoção de fósforo do efluente de um sistema convencional de lodos ativados (Estação de Tratamento de Esgotos de Barueri) pelo lodo de uma estação de tratamento de água, que utiliza sulfato de alumínio como coagulante (Estação de Tratamento de Água do Alto Cotia) e verificar a influência das seguintes variáveis nesta remoção: tempo de permanência do lodo no decantador, dosagem de lodo, potencial zeta, teor de matéria orgânica no lodo, pH da mistura lodo/efluente e uso de polímero na coagulação/floculação da água bruta. Para o desenvolvimento prático da pesquisa, foram realizados ensaios de jarros, variando as condições operacionais, de tal forma a averiguar o efeito das variáveis mencionadas anteriormente na remoção do fósforo. Observou-se que esta remoção era dependente do pH; da dosagem de lodo; do tempo de permanência do mesmo no decantador; do tempo de mistura e da presença de polímero. Independia do potencial zeta e do tempo de sedimentação. A máxima remoção obtida foi de 100% (concentração inicial de 2,9 mg P/L), em pH de 4,5, com dosagem de 37 mg lodo/L, tempo de mistura de 15 minutos a 40 s-1 de gradiente, tempo de sedimentação de 30 minutos, tempo de permanência do lodo no decantador de 80 dias, sem polímero. Nestas condições, a concentração de fósforo do efluente tratado foi de 0,01mg P/L. Os resultados obtidos no presente trabalho sinalizam uma alternativa tecnológica, que pode vir a ser utilizada em projetos sustentáveis, em que as estações de tratamento de esgotos e estações de tratamento de água sejam planejadas de forma integrada, considerando o reaproveitamento e encaminhamento do lodo de ETA como insumo a ser utilizado no fim do processo de tratamento de esgotos para remoção de fósforo do efluente final, em consonância com os conceitos de produção mais limpa na busca da qualidade. / Phosphorus is considered as the main responsible for the nutritional enrichment of reservoirs of public drinking water supplies, because eutrophication process has resulted in toxic algae blooms, and therefore its removal has a great significance since these toxins represent a public health risk and environment. The aim of this research work was to evaluate the efficiency of removal of phosphate from activated sludge process (Barueri Wastewater Treatment Plant) by sludge from water treatment plant that uses aluminum sulfate as coagulant (WTP Alto Cotia) and verify the influence of following operational parameters in this removal: aging of sludge, sludge dose, zeta potential, mixing time, sedimentation time, concentration of organic matter, pH and use of polymer in coagulation/flocculation process. For the experimental research, the jar tests were operated with different conditions. The removal of phosphate was dependent of pH, sludge dose, aging of sludge, mixing time and presence of polymer. It was independent of zeta potential and sedimentation time. It was verified that maximum efficiency of phosphate removal was around 100% (initial concentration = 2,9 mgP/L), in pH 4,5 with the use of 37 mg of sludge from Alto Cotia Water Treatment Plant per liter of effluent from Barueri Wastewater Treatment Plant, with a mixing time of 15 minutes at 40 s-1, 30 minutes for sedimentation time, 80 days for aging of sludge, without polymer. Under these conditions it was obtained phosphate concentrations around 0,01mgP/L. Results obtained in this research work show a technological alternative, that can be used in projects, that sewage and water treatment plants can be planned together, considering the reuse and forwarding the water treatment plant sludge as beneficial use in the end of the sewage treatment process for the phosphorus removal, in consonance with concepts of a cleaner production practices in Environmental Management Systems.

Grande parte do lodo gerado em ETAs no Brasil ainda é disposta em rios ou em aterros sanitários. Contudo, principalmente em grandes centros urbanos, condições de licenciamento ambiental restritivas e custos logísticos crescentes tem levantado interesse em usos benéficos para esse resíduo. Um obstáculo para a mudança de paradigma recai no fato de que muito raramente operadores e projetistas de ETAs nacionais conseguirem prever, com algum grau de confiabilidade, a massa e volume de resíduos produzidos pelo tratamento da água bruta. Geralmente, usa-se para esse fim fórmulas empíricas, que relacionam a produção de lodo à concentração de sólidos em suspensão totais (SST) na água bruta e à dosagem de produtos químicos. Os objetivos deste trabalho são: comparar o desempenho de dois dos principais métodos quantitativos de estimativa de produção de lodo o método de fórmulas empíricas, e o do balanço de massa; investigar a prática disseminada de se estimar a concentração de sólidos em suspensão totais na água bruta por meio de modelos de regressão linear com a turbidez como variável independente; e delinear condições para a aplicação dessa correlação. Foram utilizados dados de seis ETAs de ciclo completo operadas pela SABESP (ABV, Alto Cotia, Cubatão, Guaraú, Franca e Presidente Prudente), além de dados de monitoramento de 130 estações de monitoramento de águas superficiais da CETESB. Os resultados sugerem que a identificação de correlações significativas entre concentração de SST e turbidez é elusiva, e não constitui tarefa trivial. Do universo de 130 estações da CETESB, somente 7 apresentaram correlação significativa; das ETAs, somente Presidente Prudente. Modelos de regressão alternativos utilizando outras variáveis (cor, vazão média mensal e mês), combinadas com a turbidez ou isoladamente, foram desenvolvidos. Somente a inclusão do mês como variável categórica foi capaz de aumentar o poder explicativo do modelo baseado exclusivamente na turbidez, sugerindo que a relação entre turbidez e concentração de SST é variável sazonalmente. Mediante a comparação com balanços de massa, foram identificados alguns fatores que afetam o poder de predição da fórmula empírica desenvolvida pela American Water Works Association, algumas vezes de maneira drástica. Em geral, conclui-se que o uso de fórmulas empíricas principalmente em conjunto com modelos de regressão entre concentração de SST e turbidez possa não ser recomendável. / Most of the water treatment plant (WTP) residuals generated in Brazil is still discharged in water bodies, or disposed of in landfills. However, especially in large urban areas, ever stringent conditions for environmental permits e rising logistical costs have put into focus beneficial uses for those residuals. A major obstacle for paradigm change in that aspect lies in the fact that very rarely water treatment plant operators and designers are able to predict with some degree of certainty the mass and volume of residuals produced by the treatment process. Usually, empirical formulas are used for that end, which relates the residuals production rate to the concentration of total suspended solids (TSS) in the raw water, and the chemicals dose. The objectives of this work are: to compare the performance of two of the main quantitative estimation methods for residuals production the empirical formulas and the mass balance; to investigate the widespread practice of estimating the concentration of TSS using turbidity as a surrogate; and to identify the conditions under which such procedure is acceptable. For that end, data from six WTPs operated by SABESP (ABV, Alto Cotia, Cubatão, Guaraú, Franca e Presidente Prudente), plus 130 surface water monitoring stations operated by CETESB, was analyzed. Alternative regression models, employing other independent variables (color, average monthly flow and month) singly or in combination with turbidity, were developed. Only the inclusion of the month as a categorical variable was capable of enhancing the explaining power of the turbidity model, suggesting that the relation between turbidity and TSS concentration is seasonally variable. The results suggest that identification of such significant correlations between TSS concentration and turbidity is elusive at best, and doesn\'t amount to a trivial task. Out of the universe of 130 monitoring stations, in only 7 a good degree of correlation was found; of the WTPs, that was the case only in Presidente Prudente. Through the comparison with the mass balances, some factors that affect the predictive power of the American Water Works Association sometimes drastically a were identified. In general, it is concluded that the use of empirical formulas especially when combined with turbidity and TSS concentration regression models may not be recommended.

O estudo dos fatores intervenientes, micro e macropropriedades dos lodos de estação de tratamento de água (ETA), no desaguamento por sistemas naturais, com uso de leito de drenagem, constituiu o principal foco desta pesquisa. Assim, ensaios de desaguamento por leito de drenagem foram realizados com amostras de lodos de sulfato de alumínio e de cloreto de polialumínio (PA\'CL\') e monitoramento das variáveis climáticas. Os resultados comprovaram o desempenho do leito de drenagem para redução de volume, da ordem de 80% e 90% para os lodos de PA\'CL\' e sulfato de alumínio e teor de sólidos final respectivamente de 30 a 90%, sem consumo de energia. Na fase de drenagem, independente do tipo e volume de lodo aplicado, a vazão de drenagem foi maior quanto menor o valor da taxa de aplicação de sólidos - TAS (Kg/\'M POT.2\') (fração volumétrica de partículas). As variáveis analisadas, teor de sólidos, distribuição de tamanho de partículas, morfologia e composição das partículas entre outros, na massa de lodo bruto e desaguado indicaram diferentes mecanismos de secagem e conseqüente influencia na velocidade de secagem. O uso do fluxo de massa de água evaporada revelou-se adequado para avaliar a fase de secagem. O estudo das micro e macropropriedades do lodo mostram-se decisivos para balisarem pesquisas de desenvolvimento dos sistemas de desaguamento e de reúso dos lodos de ETAs. / The study of involved factors, micro and macroproperties of sludge from water treatment plants (WTP) in dewatering by natural systems with the use of draining beds is the main focus of this research. For this purpose, dewatering assays by draining beds were done with samples from aluminium sulphate and polyaluminium chloride (PA\'CL\') sludge, and monitoring of the climatic variables along the experiments. The results proved the performance of the draining beds in reducing the volume, ranging from 80 to 90% for the sludges from PA\'CL\' and aluminium sulphate and the final rate of solids from 30 to 90%, without consuming the energy. In dewatering phase, independently of the type and volume of the applied sludge, the bigger the flow of dewatering the lesser the value of the applied rate of solids (TAS, Kg/\'M POT.2\', volumetric fraction of particles). The analised variables, solid rates, distribution of the height of the particles, morphology, and composition of the particles among others, in the mass of the brute and dewatered sludge indicated different mechanisms of drying and consequently influence in the rate of drying. The use of the flow of mass of humidity revealed adequate to evaluate the drying phase. The studies of micro and macroproperties of the sludge were decisive to conduct researches of development of dewatering systems and reusing of the sludges from WTP´s.

Made available in DSpace on 2016-08-10T10:55:44Z (GMT). No. of bitstreams: 1 Aurelio de Melo Barbosa.pdf: 8372928 bytes, checksum: 34ed59e6bd218f99a1d12f2d2abdaa9e (MD5) Previous issue date: 2009-03-30 / Water, essential for life, has a direct influence on health, quality of life and development of mankind. However, due to natural and human causes, water may suffer contamination from various species, especially for chemical elements. Thus, this paper appears the results of a study of multi-elemental chemical analysis of samples of treated water collected in Water Treatment Plants of twenty-two cities of South Region of Goias State. It was also exposes data on sanitation and hospital morbidity and mortality of the study area. It was found two geochemical associations (SO4-Cl-Zn-Mn and Ca-Sr-Mg), that were presented in maps of distribution of each element geochemistry. Also it was found anomalous concentrations above the maximum permitted values of nitrate in samples of Quirinópolis and Morrinhos, and lead in the sample of Cromínia, with possible impact on the morbidity and mortality of these municipalities. / A água, essencial para a vida, tem influência direta sobre a saúde, qualidade de vida e desenvolvimento do ser humano. Entretanto, devido a causas naturais e antrópicas, a água pode sofrer contaminação de várias espécies, especialmente por elementos químicos. Assim, realizou-se um estudo de análise química multielementar de amostras de água tratada colhidas em Estações de Tratamento de Água de vinte e dois municípios da Mesorregião Sul Goiano. Também foram coletados dados sobre saneamento básico e morbidade hospitalar e mortalidade da área de estudo. Como resultado foram encontradas duas associações geoquímicas (Cl-Zn-SO4-Mn e Ca-Sr-Mg), sendo apresentados os mapas de distribuição geoquímica de cada elemento. Também descobriu-se concentrações anômalas, acima dos Valores Máximos Permitidos, de nitrato nas amostras de Quirinópolis e Morrinhos, e de chumbo na amostra de Cromínia, com possível impacto sobre a morbimortalidade dos referidos municípios.

Cette thèse porte sur le comportement d’un composé prioritaire au titre de la Directive Cadre sur l’Eau au niveau européen : le tributylétain (TBT) et ses métabolites (dibutylétain (DBT) et monobutylétain (MBT)). On s’intéresse plus particulièrement aux eaux usées domestiques lors de leur transit dans deux stations d’épuration par lagunage naturel (STEP), traitement adapté aux effluents provenant des zones faiblement urbanisées. Ce travail de thèse vient combler le manque de résultats scientifiques sur (1) le niveau des concentrations en butylétains dans les effluents domestiques des zones peu urbanisées en entrée des stations par lagunage et en sortie après traitement ; (2) l’efficacité du traitement par lagunage à éliminer les butylétains ; (3)l’identification des processus qui contrôlent le devenir de ces éléments au cours du traitement.Les butylétains sont mesurés dans les matrices particulaires, dissoutes et dans les boues, par couplage GC-ICP-MS, dans toutes les étapes du traitement par lagunage de deux communes rurales du département de l’Hérault (34,France) : Gigean (6000 eq-hab.) et Montbazin (4500 eq-hab.). On montre que les trois espèces butylées sont systématiquement présentes dans tous les échantillons prélevés sur les deux STEP. Les butylétains arrivent principalement sous forme particulaire dans les eaux brutes en entrée des stations. Au cours du traitement, les processus de sorption sur les particules en suspension et la décantation de ces dernières au fond de chaque bassin sont les principaux facteurs permettant l’élimination des butylétains. Les premiers bassins anaérobies, de grande profondeur et de long temps de séjour, permettent l’élimination de plus de 60% à Gigean (93% à Montbazin) des butylétains. Les boues de fond de chaque bassin montrent des concentrations élevées en butylétains. La remise en suspension des butylétains est notée dans les derniers bassins de finition, peu profonds, ce qui peut être due à la re-stratification thermique. En sortie de station, malgré les abattements importants, des concentrations non négligeables en butylétains (12 à 228 et 1.8 à 15 ng(Sn).L-1 respectivement pour Montbazin et Gigean) sont rejetées dans le milieu récepteur. Des expériences de sorption basées sur la mise en contact de butylétains avec des boues de fond de bassin diluées ont été effectuées selon plusieurs approches expérimentales. On a ainsi montré que (1) la distribution des espèces MBT, DBT, TBT, entre les phases solide et liquide, est variable d’un test à l’autre selon les conditions opératoires ; (2) l’affinité entre les butylétains et la boue est importante, quelle que soit sa provenance. 98% des butylétains se retrouvent dans la phase solide, du fait de leur hydrophobicité. Le coefficient de distribution Kd entre le TBT et les boues est plus élevé que celui obtenu pour d’autres type de phases solides (75000 L.kg- 1) ; (3) le processus de sorption est rapide. De plus des processus de sorption, désorption et déalkylation du TBT, expliquant les variations des concentrations en MBT et DBT dans la phase solide ont été identifiés. La désorption du TBT est rapide. Il se dégrade dans la phase liquide en DBT dont une partie se transforme en MBT. La sorption du MBT sur les boues a été systématiquement mesurée. Le phénomène de sorption n’est donc pas complètement réversible au cours du temps. Ces résultats contribuent à expliquer les dysfonctionnements observés dans les stations de traitement par lagunage, par exemple lors d’apports directs d’eau de pluie.Cette thèse démontre la présence systématique des butylétains dans les stations d’épuration par lagunage naturel. Les données acquises in-situ couplées à des essais en laboratoire permettent de comprendre le comportement de ces composés lors de ce traitement : la fraction solide joue un rôle clé dans les processus de sorption-désorption-(bio)dégradation des butylétains. / This thesis deals with the behavior of a priority compound on the basis of the framework Directive on water at European level: tributyltin (TBT) ) and its metabolites (dibutyltin (DBT) and monobutyltin (MBT)). The study is focused on two waste stabilization pond treatment plants (WSP), which is an appropriate treatment to domestic effluents from sparsely urbanized areas.This thesis comes to fill the lack of scientific results on (1) the level of butyltin concentrations in domestic effluents from sparsely urbanized areas, in the input of the WSP and the output after treatment; (2) the efficiency of butyltins elimination by the WSP treatment; (3) the identification of the processes that control the fate of these elements during the treatment.Butyltins are measured in particulate and dissolved matrices and in sludge, by GC-ICP-MS, in all stages of the treatment by lagooning of two villages of the Department of Hérault (34, France): Gigean (6000 p.e.) and Montbazin (4500 p.e.).It is shown that the three butyltin species are consistently present in all samples taken from the two WSP. Butyltins arrive primarily in particulate form in the raw water. During treatment, the processes of sorption onto particulate matter and the settling of the latter at the bottom of each basin are the main factors for the elimination of butyltins. The first anaerobic ponds, characterized by deep depth and long residence times, allow the elimination of more than 60% Gigean (93% at Montbazin) of butyltins. Bottom sludge of each basin show high butyltins concentrations. The resuspension of butyltins is noted in the last maturation ponds, characterized by shallow depth, which may be due to re-thermal stratification. At the outlet, despite significant butyltin removal, concentrations in butyltins remain high (12 to 228 and 1.8 to 15 ng (Sn). L-1, respectively for Montbazin and Gigean).Laboratory batch experiments were conducted to study sorption processes following several experimental protocols. It was thus shown that: (1) the distribution of the butyltin species between solid and liquid phases is different from one test to another according to the operating conditions; (2) the affinity between butyltins and bottom sludge is important, regardless of its provenance. 98% of the butyltins are found in the solid phase, due to their hydrophobicity. The TBT sludge-water partition coefficient is higher than that obtained for other type of solid phases (75000 L.kg-1); (3) the process of sorption is fast.Moreover processes of sorption, desorption and dealkylation of TBT, explaining changes in concentrations of MBT and DBT in the solid phase were identified. Desorption of TBT is fast. It degrades in the liquid phase in DBT which part turns into MBT. The sorption of MBT on sludge has been systematically measured. Therefore, the sorption phenomenon is not completely reversible over time. These results help to explain the dysfunctions observed in WSP, for example after direct inputs of rainwater.This thesis shows the systematic presence of butyltin in waste stabilization pond treatment plants. In-situ data coupled with laboratory tests allow to understand the behaviour of these compounds during this treatment: the solid fraction plays a key role in the processes of sorption-desorption-(bio) degradation of butyltins.

Submitted by Mariana Dornelles Vargas (marianadv) on 2015-04-10T19:29:16Z No. of bitstreams: 1 influencia_variabilidade.pdf: 2460487 bytes, checksum: 14d53357bd40cb3e9c4c2a4ec2ac0ec8 (MD5) / Made available in DSpace on 2015-04-10T19:29:16Z (GMT). No. of bitstreams: 1 influencia_variabilidade.pdf: 2460487 bytes, checksum: 14d53357bd40cb3e9c4c2a4ec2ac0ec8 (MD5) Previous issue date: 2014-11-27 / Nenhuma / As estações de tratamento de água (ETA) são consideradas fontes de poluição, por gerarem resíduos sólidos como subproduto do próprio processo de tratamento. Por falta de adoção das políticas específicas de gerenciamento pelas ETAS, o lodo de estação de tratamento de água (LETA) tem sido disposto de forma ambientalmente inadequada, em cursos d'água. Uma alternativa viável seria a utilização deste LETA na fabricação de cerâmica vermelha destinada a construção civil, sendo assim, este trabalho tem por objetivo avaliar a influência da composição química do LETA, alterado pela qualidade da água a ser tratada, nas propriedades de cerâmica vermelha produzidas com este resíduo. Para atingir a finalidade proposta utilizaram-se 3 amostras de LETA, coletadas em Agosto de 2013, Dezembro de 2013 e Março de 2014 e uma amostra de argila, que foi amostrada em uma Olaria localizada em Porto Alegre – RS. A metodologia dividiu-se em coleta e caracterização das matérias primas, produção das 4 cerâmicas diferentes e caracterização das propriedades químicas, físicas e mecânicas das cerâmicas. O LETA foi prensado com adição de Cal para a retirada de excesso de água em um filtro prensa e caracterizado por meio dos ensaios de sólidos totais, fixos e voláteis, FRX, DRX, solubilização e lixiviação. Na argila, o LETA prensado foi empregado em adição de 5% em relação à massa total e então homogeneizado para a realização da extrusão dos corpos de prova. Os corpos de prova foram sinterizados em forno mufla nas temperaturas de 800°C, 950°C e 1050°C. As cerâmicas foram caracterizadas quanto à composição química e mineralógica, perda ao fogo e caracterização ambiental. Analisou-se a retração linear, a absorção de água e resistência à flexão dos corpos de prova. A composição química do LETA apresentou influência significativa nas propriedades estudadas das cerâmicas sinterizadas à 950ᵒC e 1050ᵒC, sendo que a propriedade mais afetada foi a absorção de água inicial sinterizada em 950ᵒC, obtendo-se um acréscimo de 61% nos corpos de prova B e 12% nos corpos de prova CPD em relação as cerâmicas de referência. Na temperatura de 1050ºC as cerâmicas apresentaram problema de baixa absorção de água. Nas cerâmicas sinterizadas à 800ºC as propriedades físicas e mecânicas não foram alteradas significativamente pela adição de lodo, mostrando-se viável a adição de LETA na cerâmica sinterizada nesta temperatura. / The water treatment plants (WTP) are considered point sources of pollution, for generating solid waste as a byproduct of the treatment process itself. For lack of adoption of specific management policies by WTP, the WTS has been disposed of improperly in environmentally watercourses. A viable alternative would be to use this WTS in the manufacture of red ceramic intended for construction, so this work aims to evaluate the influence of the chemical composition of the WTS, as amended by the water quality be treated in the properties of red pottery produced with this residue. To reach the proposed aim we used three samples of WTS, collected in August 2013, December 2013 and March 2014 and a sample of clay, which was sampled in a Pottery located in Porto Alegre - RS. The methodology divided into collecting and characterization of raw materials, production of 4 ceramics and characterization of different chemical, physical and mechanical properties of ceramics. The WTS was pressed with addition of lime for the removal of excess water and characterized by means of tests solids, fixed and volatile, XRF, XRD, solubilization and leaching. In clay, the WTS go been employed in addition of 5% relative to the total mass, and then homogenized for carrying out the extrusion of test specimens. The specimens were sintered in a muffle furnace at temperatures of 800°C, 950°C and 1050°C. The ceramics were characterized for chemical and mineralogical composition, loss on ignition and environmental characterization. We analyzed the linear shrinkage, water absorption and flexural strength of the ceramics. The chemical composition of WTS significantly affecting the properties of the ceramic sintered on 950ᵒC and 1050ᵒC, being the most affected absorption property was on 950ᵒC the initial water absorption, yielding an increase of 61% in the specimens CPB and 12 % CPD in the samples in relation to the reference ceramic. On the temperature 1050ºC, presented low water absorption. In the ceramics sintered at 800 ° C the physical and mechanical properties were not change significantly by the addition of sludge, being feasible the addition of WTS in this temperature.

O fósforo é apontado como o principal responsável pelo enriquecimento nutricional de mananciais de abastecimento público, desencadeando por meio do fenômeno de eutrofização, a floração de grupos algais tóxicos e, portanto a sua remoção passa a ter grande significado para a saúde pública e para o meio ambiente. O presente trabalho foi desenvolvido com os objetivos de: avaliar a eficiência de remoção de fósforo do efluente de um sistema convencional de lodos ativados (Estação de Tratamento de Esgotos de Barueri) pelo lodo de uma estação de tratamento de água, que utiliza sulfato de alumínio como coagulante (Estação de Tratamento de Água do Alto Cotia) e verificar a influência das seguintes variáveis nesta remoção: tempo de permanência do lodo no decantador, dosagem de lodo, potencial zeta, teor de matéria orgânica no lodo, pH da mistura lodo/efluente e uso de polímero na coagulação/floculação da água bruta. Para o desenvolvimento prático da pesquisa, foram realizados ensaios de jarros, variando as condições operacionais, de tal forma a averiguar o efeito das variáveis mencionadas anteriormente na remoção do fósforo. Observou-se que esta remoção era dependente do pH; da dosagem de lodo; do tempo de permanência do mesmo no decantador; do tempo de mistura e da presença de polímero. Independia do potencial zeta e do tempo de sedimentação. A máxima remoção obtida foi de 100% (concentração inicial de 2,9 mg P/L), em pH de 4,5, com dosagem de 37 mg lodo/L, tempo de mistura de 15 minutos a 40 s-1 de gradiente, tempo de sedimentação de 30 minutos, tempo de permanência do lodo no decantador de 80 dias, sem polímero. Nestas condições, a concentração de fósforo do efluente tratado foi de 0,01mg P/L. Os resultados obtidos no presente trabalho sinalizam uma alternativa tecnológica, que pode vir a ser utilizada em projetos sustentáveis, em que as estações de tratamento de esgotos e estações de tratamento de água sejam planejadas de forma integrada, considerando o reaproveitamento e encaminhamento do lodo de ETA como insumo a ser utilizado no fim do processo de tratamento de esgotos para remoção de fósforo do efluente final, em consonância com os conceitos de produção mais limpa na busca da qualidade. / Phosphorus is considered as the main responsible for the nutritional enrichment of reservoirs of public drinking water supplies, because eutrophication process has resulted in toxic algae blooms, and therefore its removal has a great significance since these toxins represent a public health risk and environment. The aim of this research work was to evaluate the efficiency of removal of phosphate from activated sludge process (Barueri Wastewater Treatment Plant) by sludge from water treatment plant that uses aluminum sulfate as coagulant (WTP Alto Cotia) and verify the influence of following operational parameters in this removal: aging of sludge, sludge dose, zeta potential, mixing time, sedimentation time, concentration of organic matter, pH and use of polymer in coagulation/flocculation process. For the experimental research, the jar tests were operated with different conditions. The removal of phosphate was dependent of pH, sludge dose, aging of sludge, mixing time and presence of polymer. It was independent of zeta potential and sedimentation time. It was verified that maximum efficiency of phosphate removal was around 100% (initial concentration = 2,9 mgP/L), in pH 4,5 with the use of 37 mg of sludge from Alto Cotia Water Treatment Plant per liter of effluent from Barueri Wastewater Treatment Plant, with a mixing time of 15 minutes at 40 s-1, 30 minutes for sedimentation time, 80 days for aging of sludge, without polymer. Under these conditions it was obtained phosphate concentrations around 0,01mgP/L. Results obtained in this research work show a technological alternative, that can be used in projects, that sewage and water treatment plants can be planned together, considering the reuse and forwarding the water treatment plant sludge as beneficial use in the end of the sewage treatment process for the phosphorus removal, in consonance with concepts of a cleaner production practices in Environmental Management Systems.

Grande parte do lodo gerado em ETAs no Brasil ainda é disposta em rios ou em aterros sanitários. Contudo, principalmente em grandes centros urbanos, condições de licenciamento ambiental restritivas e custos logísticos crescentes tem levantado interesse em usos benéficos para esse resíduo. Um obstáculo para a mudança de paradigma recai no fato de que muito raramente operadores e projetistas de ETAs nacionais conseguirem prever, com algum grau de confiabilidade, a massa e volume de resíduos produzidos pelo tratamento da água bruta. Geralmente, usa-se para esse fim fórmulas empíricas, que relacionam a produção de lodo à concentração de sólidos em suspensão totais (SST) na água bruta e à dosagem de produtos químicos. Os objetivos deste trabalho são: comparar o desempenho de dois dos principais métodos quantitativos de estimativa de produção de lodo o método de fórmulas empíricas, e o do balanço de massa; investigar a prática disseminada de se estimar a concentração de sólidos em suspensão totais na água bruta por meio de modelos de regressão linear com a turbidez como variável independente; e delinear condições para a aplicação dessa correlação. Foram utilizados dados de seis ETAs de ciclo completo operadas pela SABESP (ABV, Alto Cotia, Cubatão, Guaraú, Franca e Presidente Prudente), além de dados de monitoramento de 130 estações de monitoramento de águas superficiais da CETESB. Os resultados sugerem que a identificação de correlações significativas entre concentração de SST e turbidez é elusiva, e não constitui tarefa trivial. Do universo de 130 estações da CETESB, somente 7 apresentaram correlação significativa; das ETAs, somente Presidente Prudente. Modelos de regressão alternativos utilizando outras variáveis (cor, vazão média mensal e mês), combinadas com a turbidez ou isoladamente, foram desenvolvidos. Somente a inclusão do mês como variável categórica foi capaz de aumentar o poder explicativo do modelo baseado exclusivamente na turbidez, sugerindo que a relação entre turbidez e concentração de SST é variável sazonalmente. Mediante a comparação com balanços de massa, foram identificados alguns fatores que afetam o poder de predição da fórmula empírica desenvolvida pela American Water Works Association, algumas vezes de maneira drástica. Em geral, conclui-se que o uso de fórmulas empíricas principalmente em conjunto com modelos de regressão entre concentração de SST e turbidez possa não ser recomendável. / Most of the water treatment plant (WTP) residuals generated in Brazil is still discharged in water bodies, or disposed of in landfills. However, especially in large urban areas, ever stringent conditions for environmental permits e rising logistical costs have put into focus beneficial uses for those residuals. A major obstacle for paradigm change in that aspect lies in the fact that very rarely water treatment plant operators and designers are able to predict with some degree of certainty the mass and volume of residuals produced by the treatment process. Usually, empirical formulas are used for that end, which relates the residuals production rate to the concentration of total suspended solids (TSS) in the raw water, and the chemicals dose. The objectives of this work are: to compare the performance of two of the main quantitative estimation methods for residuals production the empirical formulas and the mass balance; to investigate the widespread practice of estimating the concentration of TSS using turbidity as a surrogate; and to identify the conditions under which such procedure is acceptable. For that end, data from six WTPs operated by SABESP (ABV, Alto Cotia, Cubatão, Guaraú, Franca e Presidente Prudente), plus 130 surface water monitoring stations operated by CETESB, was analyzed. Alternative regression models, employing other independent variables (color, average monthly flow and month) singly or in combination with turbidity, were developed. Only the inclusion of the month as a categorical variable was capable of enhancing the explaining power of the turbidity model, suggesting that the relation between turbidity and TSS concentration is seasonally variable. The results suggest that identification of such significant correlations between TSS concentration and turbidity is elusive at best, and doesn\'t amount to a trivial task. Out of the universe of 130 monitoring stations, in only 7 a good degree of correlation was found; of the WTPs, that was the case only in Presidente Prudente. Through the comparison with the mass balances, some factors that affect the predictive power of the American Water Works Association sometimes drastically a were identified. In general, it is concluded that the use of empirical formulas especially when combined with turbidity and TSS concentration regression models may not be recommended.

The environmental occurrence and behaviour of the brominated flame retardant (BFR) decabromodiphenyl ethane (dbdpe) has only been studied to a limited extent. It is structurally similar to decabromodiphenyl ether (decaBDE), which makes it conceivable that dbdpe may also become an environmental contaminant of concern. A method for environmental analysis and comparative assessments of dbdpe and decaBDE was developed. Both BFRs were studied in: a mass balance of the Henriksdal WWTP in Stockholm (Paper I); an international survey of sewage sludge (Paper II); sediment along a transect from Henriksdal WWTP to the outer archipelago of Stockholm and from isolated Swedish lakes (Paper III); and a benthic food web from the Scheldt estuary (Paper IV). Dbdpe was found in sludge from every country surveyed, indicating that it may be a worldwide concern. The WWTP mass balance showed that virtually all of the BFRs were transferred from wastewater to sludge. A small fraction was emitted via the effluent, confirming emissions to the aquatic environment. In the marine sediment, the BFR levels close to the WWTP outfall were high. They decreased along the transect to low levels in the outer archipelago. The study of lake sediment showed a widespread presence of dbdpe in the Swedish environment and provided evidence that it originates from long range atmospheric transport. In the food web, dbdpe did bioaccumulate to a small extent which was similar to decaBDE. The transfer of the BFRs from sediment to benthic invertebrates was low, while transfer from prey to predator was higher. Biodilution was observed rather than biomagnification. This work suggests that the persistence, the susceptibility to long range atmospheric transport, and the potential for bioaccumulation are similar for dbdpe and the regulated decaBDE that it is replacing. Thus, there is a risk that a problematic environmental pollutant is being replaced with a chemical that is equally problematic. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 4: Manuscript.