The active synthetic constituent of oral contraceptives 17α- ethinylestradiol (EE2) and its natural steroidal estrogen analogues are being released into the aquatic environment mainly via wastewater treatment plants (WWTPs). Although steroidal estrogens have been frequently reported in very low concentrations in the environment, they have been placed at the top of the list of endocrine disrupting chemicals (EDCs) for their high estrogenic activity in non-target aquatic species like fish and frogs. Almost 30 years worth of intensive research has moved the problem of endocrine disruption in the aquatic environment from being a hypothesis to a well-known cause-and-effect story. However, the fate and effects of many pharmaceuticals, including EE2, remain poorly understood. Thus, the main objective of this thesis was to investigate EE2 bioaccumulation in fish by field and laboratory studies. An optimized sample preparation and analytical method protocol was achieved to detect EE2 in its biologically active form in whole fish tissue at trace levels (ng/g). Shorthead redhorse suckers (ShRHS) (Moxostoma macrolepidotum) collected in proximity to a WWTP in the St. Clair River have significantly accumulated EE2 with an average of 1.5 ng/g. EE2 bioaccumulation was limited to fish exhibiting intersex and with induced vitellogenin (VTG). EE2 was absent in fish from a reference site. Positive correlations between EE2 and lipid content as well as "15N supported the hypothesis of EE2 bioaccumulation in wild ShRHSs. A wider survey was carried out to explore patterns of EE2 bioaccumulation in the pelagic and benthic food-wed of the St. Clair IV River, Ontario. In the WWTP effluents and nearby surface waters, EE2 levels were extremely low and below our method detection limits. All of the seven sampled species from different trophic levels and the sediment samples collected from the impacted sites and the reference sites did not have any measurable EE2 concentrations. A laboratory controlled study where male goldfish (Carassius auratus) were exposed to EE2 via water versus food demonstrated that fish can rapidly accumulate EE2 by both routes of exposure. The uptake constant for water was 45 h-1 and the bioconcentration factor for EE2 in fish was 377. The fast uptake rate of EE2 via water coincided with a much slower elimination rate constant of 0.0786 h-1. The assimilation efficiency of 0.106 for EE2 by goldfish was determined by EE2 dietary exposure, which was used to predict EE2 accumulation under different exposure scenarios. The work presented here was the first demonstration of EE2 bioaccumulation in wild fish and the first to model EE2 bioaccumulation from water and dietary exposure in laboratory-exposed fish.

The active synthetic constituent of oral contraceptives 17α- ethinylestradiol (EE2) and its natural steroidal estrogen analogues are being released into the aquatic environment mainly via wastewater treatment plants (WWTPs). Although steroidal estrogens have been frequently reported in very low concentrations in the environment, they have been placed at the top of the list of endocrine disrupting chemicals (EDCs) for their high estrogenic activity in non-target aquatic species like fish and frogs. Almost 30 years worth of intensive research has moved the problem of endocrine disruption in the aquatic environment from being a hypothesis to a well-known cause-and-effect story. However, the fate and effects of many pharmaceuticals, including EE2, remain poorly understood. Thus, the main objective of this thesis was to investigate EE2 bioaccumulation in fish by field and laboratory studies. An optimized sample preparation and analytical method protocol was achieved to detect EE2 in its biologically active form in whole fish tissue at trace levels (ng/g). Shorthead redhorse suckers (ShRHS) (Moxostoma macrolepidotum) collected in proximity to a WWTP in the St. Clair River have significantly accumulated EE2 with an average of 1.5 ng/g. EE2 bioaccumulation was limited to fish exhibiting intersex and with induced vitellogenin (VTG). EE2 was absent in fish from a reference site. Positive correlations between EE2 and lipid content as well as "15N supported the hypothesis of EE2 bioaccumulation in wild ShRHSs. A wider survey was carried out to explore patterns of EE2 bioaccumulation in the pelagic and benthic food-wed of the St. Clair IV River, Ontario. In the WWTP effluents and nearby surface waters, EE2 levels were extremely low and below our method detection limits. All of the seven sampled species from different trophic levels and the sediment samples collected from the impacted sites and the reference sites did not have any measurable EE2 concentrations. A laboratory controlled study where male goldfish (Carassius auratus) were exposed to EE2 via water versus food demonstrated that fish can rapidly accumulate EE2 by both routes of exposure. The uptake constant for water was 45 h-1 and the bioconcentration factor for EE2 in fish was 377. The fast uptake rate of EE2 via water coincided with a much slower elimination rate constant of 0.0786 h-1. The assimilation efficiency of 0.106 for EE2 by goldfish was determined by EE2 dietary exposure, which was used to predict EE2 accumulation under different exposure scenarios. The work presented here was the first demonstration of EE2 bioaccumulation in wild fish and the first to model EE2 bioaccumulation from water and dietary exposure in laboratory-exposed fish.

The active synthetic constituent of oral contraceptives 17α- ethinylestradiol (EE2) and its natural steroidal estrogen analogues are being released into the aquatic environment mainly via wastewater treatment plants (WWTPs). Although steroidal estrogens have been frequently reported in very low concentrations in the environment, they have been placed at the top of the list of endocrine disrupting chemicals (EDCs) for their high estrogenic activity in non-target aquatic species like fish and frogs. Almost 30 years worth of intensive research has moved the problem of endocrine disruption in the aquatic environment from being a hypothesis to a well-known cause-and-effect story. However, the fate and effects of many pharmaceuticals, including EE2, remain poorly understood. Thus, the main objective of this thesis was to investigate EE2 bioaccumulation in fish by field and laboratory studies. An optimized sample preparation and analytical method protocol was achieved to detect EE2 in its biologically active form in whole fish tissue at trace levels (ng/g). Shorthead redhorse suckers (ShRHS) (Moxostoma macrolepidotum) collected in proximity to a WWTP in the St. Clair River have significantly accumulated EE2 with an average of 1.5 ng/g. EE2 bioaccumulation was limited to fish exhibiting intersex and with induced vitellogenin (VTG). EE2 was absent in fish from a reference site. Positive correlations between EE2 and lipid content as well as "15N supported the hypothesis of EE2 bioaccumulation in wild ShRHSs. A wider survey was carried out to explore patterns of EE2 bioaccumulation in the pelagic and benthic food-wed of the St. Clair IV River, Ontario. In the WWTP effluents and nearby surface waters, EE2 levels were extremely low and below our method detection limits. All of the seven sampled species from different trophic levels and the sediment samples collected from the impacted sites and the reference sites did not have any measurable EE2 concentrations. A laboratory controlled study where male goldfish (Carassius auratus) were exposed to EE2 via water versus food demonstrated that fish can rapidly accumulate EE2 by both routes of exposure. The uptake constant for water was 45 h-1 and the bioconcentration factor for EE2 in fish was 377. The fast uptake rate of EE2 via water coincided with a much slower elimination rate constant of 0.0786 h-1. The assimilation efficiency of 0.106 for EE2 by goldfish was determined by EE2 dietary exposure, which was used to predict EE2 accumulation under different exposure scenarios. The work presented here was the first demonstration of EE2 bioaccumulation in wild fish and the first to model EE2 bioaccumulation from water and dietary exposure in laboratory-exposed fish.

The active synthetic constituent of oral contraceptives 17α- ethinylestradiol (EE2) and its natural steroidal estrogen analogues are being released into the aquatic environment mainly via wastewater treatment plants (WWTPs). Although steroidal estrogens have been frequently reported in very low concentrations in the environment, they have been placed at the top of the list of endocrine disrupting chemicals (EDCs) for their high estrogenic activity in non-target aquatic species like fish and frogs. Almost 30 years worth of intensive research has moved the problem of endocrine disruption in the aquatic environment from being a hypothesis to a well-known cause-and-effect story. However, the fate and effects of many pharmaceuticals, including EE2, remain poorly understood. Thus, the main objective of this thesis was to investigate EE2 bioaccumulation in fish by field and laboratory studies. An optimized sample preparation and analytical method protocol was achieved to detect EE2 in its biologically active form in whole fish tissue at trace levels (ng/g). Shorthead redhorse suckers (ShRHS) (Moxostoma macrolepidotum) collected in proximity to a WWTP in the St. Clair River have significantly accumulated EE2 with an average of 1.5 ng/g. EE2 bioaccumulation was limited to fish exhibiting intersex and with induced vitellogenin (VTG). EE2 was absent in fish from a reference site. Positive correlations between EE2 and lipid content as well as "15N supported the hypothesis of EE2 bioaccumulation in wild ShRHSs. A wider survey was carried out to explore patterns of EE2 bioaccumulation in the pelagic and benthic food-wed of the St. Clair IV River, Ontario. In the WWTP effluents and nearby surface waters, EE2 levels were extremely low and below our method detection limits. All of the seven sampled species from different trophic levels and the sediment samples collected from the impacted sites and the reference sites did not have any measurable EE2 concentrations. A laboratory controlled study where male goldfish (Carassius auratus) were exposed to EE2 via water versus food demonstrated that fish can rapidly accumulate EE2 by both routes of exposure. The uptake constant for water was 45 h-1 and the bioconcentration factor for EE2 in fish was 377. The fast uptake rate of EE2 via water coincided with a much slower elimination rate constant of 0.0786 h-1. The assimilation efficiency of 0.106 for EE2 by goldfish was determined by EE2 dietary exposure, which was used to predict EE2 accumulation under different exposure scenarios. The work presented here was the first demonstration of EE2 bioaccumulation in wild fish and the first to model EE2 bioaccumulation from water and dietary exposure in laboratory-exposed fish.

Made available in DSpace on 2017-07-24T19:38:14Z (GMT). No. of bitstreams: 1 Monalisa Santos.pdf: 2681672 bytes, checksum: c32e0b48f967016b011a1aa3693a3b59 (MD5) Previous issue date: 2014-04-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work presents a study for preparation of thin films obtained with a natural and synthetic polyelectrolyte, such as humic acid (HA) and by the hybrid prepared by encapsulation of platinum nanoparticles in the matrix of chloride 3-n- propylpyridinium silsesquioxane (Pt-SiPy+Cl-). Even when dealing with molecules of complex nature, the film deposition occurred regardless of the type of substrate. It was found that there was growth of films by alternate deposition of polyelectrolytes HA and Pt-SiPy+Cl-, governed largely by electrostatic interactions between functional groups COOH, OH-phenolic of HA with pyridinium ring of SiPy+Cl-. The presence of polyelectrolytes in LbL films built on molecular architectures (HA/Pt-SiPy+Cl-)n and (Pt-SiPy+Cl-/HA)n, was obtained by spectroscopic measurements. From the shifts of the bands in the absorption spectra in the UV-Vis region of LbL films in relation to the precursor solutions, it was inferred on the interactions between these molecules. Measurements of absorption spectroscopy FTIR and Raman scattering of the LbL film were observed by displacement or disappearance of absorption bands due to the presence of precursors of Pt-NPs cavities of SiPy+Cl-. It was found that bands were more intense and defined in the spectra of the film (HA/Pt-SiPy+Cl-)30 in relation to the (Pt-SiPy+Cl-/HA)30 film. This observation corroborates the results of UV-Vis showing that from 12 bilayers no linear growth of absorbance as a function of number of bilayers (Pt-SiPy+Cl-/HA)12. The AFM images showed a linear increase when the film (HA/Pt-SiPy+Cl-)30 was obtained with a thickness of 2.6 nm per bilayer, confirming the nanostructured nature provided by the molecular organization of polyelectrolytes. Morphological characterization showed that the homogeneity of the surface in function of the amount of deposited materials influence of surface phenomena, such as the number of active sites, as evidenced by electrochemical action of the hormone 17α - ethinylestradiol (EE2). From the diferential pulse voltammetric response of the investigated in the presence of EE2 6.25 x 10-5 mol L-1, it was found that the film (HA/Pt-SiPy+Cl-)3 showed high peak current (Ipa = 17.26 μA) and minor oxidation potential (Epa = 0,74 V vs Ag/AgCl) in relation to no modified electrode (FTO) (Ipa = 8,97 μA e Epa = 1,1 V). Under these conditions , the electrode (HA/Pt-SiPy+Cl-)3 obtained a linear response in the concentration range of 1.37 x 10-6 to 2.14 x 10-5 mol L- 1, yielding a sensitivity 0.68 mmol L-1 and limits of detection ( LOD) and quantification (LOQ ) equal to 1.06 x 10-6 and 3.52 x 10-6 mol L-1 . These values are close to those reported in the literature for electrodes modified with metals nanoparticles. Finally, the technique of electrochemical impedance spectroscopy confirmed that the sequence of deposition, the number of bilayers, as well as the nature of the nanostructured films LbL affect the charge transfer resistance. Therefore, the presence of HA in the architecture of the film decreases the charge transfer resistance of the fact that this macromolecule consist of large number of functional groups , which provide a greater number of sites occur for interactions with the pyridinium group SiPy+Cl- and consequently higher amounts of Pt-Np on the electrode surface. / Este trabalho apresenta um estudo para a obtenção de filmes finos obtidos com um polieletrólito natural e sintético, tal como o ácido húmico (AH) e o híbrido formado pela encapsulação de nanopartículas de platina na matriz de cloreto de 3-n-propilpiridínio silsesquioxano (Pt-SiPy+Cl-). Mesmo se tratando de moléculas de natureza complexas, a deposição do filme ocorreu independente do tipo do substrato. Verificou-se que houve crescimento dos filmes pela deposição alternada dos polieletrólitos AH e Pt-SiPy+Cl-, governadas em grande parte por interações eletrostáticas entre os grupos funcionais COOH, OH-fenólicos e enólicos do AH com o anel piridínio do SiPy+Cl-. A presença dos polieletrólitos nos filmes LbL construídos nas arquiteturas moleculares (AH/Pt-SiPy+Cl-)n e (Pt-SiPy+Cl-/AH)n, foi obtida por medidas espectroscópicas. A partir dos deslocamentos das bandas nos espectros de absorção na região do UV-Vis dos filmes LbL em relação às soluções precursoras, inferiu-se sobre as interações entre estas moléculas. Por medidas de espectroscopia de absorção na região do FTIR e espalhamento Raman dos filmes LbL observou-se deslocamento ou desaparecimento de bandas de absorção dos precursores devido à presença de NPs-Pt nas cavidades do SiPy+Cl-. Verificou-se que as bandas são mais intensas e definidas nos espectros do filme (AH/Pt-SiPy+Cl-)30 em relação ao filme (Pt-SiPy+Cl-/AH)30. Esta observação corrobora com resultados de UV-Vis mostrando que a partir de 12 bicamadas não há crescimento linear da absorbância em função do número de bicamadas (Pt-SiPy+Cl-/AH)n. As imagens de AFM revelaram um crescimento linear quando o filme (AH/Pt-SiPy+Cl-)30 foi obtido, com espessura de 2,6 nm por bicamada, confirmando a natureza nanoestruturada propiciada pela organização molecular dos polieletrólitos. A caracterização morfológica demonstrou que a homogeneidade da superfície em função da quantidade de material depositada influencia os fenômenos de superfície, como a quantidade de sítios ativos, fato constatado por medidas eletroquímicas do hormônio 17α-etinilestradiol (EE2). A partir das respostas voltamétricas por pulso diferencial dos sensores investigados na presença de EE2 6,25 x 10-5 mol L-1, verificou-se que o filme (AH/Pt-SiPy+Cl-)3 apresentou valores de corrente de oxidação mais intensos (Ipa = 17,26 μA) e menor potencial de oxidação (Epa = 0,74 V vs Ag/AgCl) em relação ao eletrodo não modificado (FTO) (Ipa = 8,97 μA e Epa = 1,1 V). Nestas condições, o eletrodo (AH/Pt-SiPy+Cl-)3 obteve uma resposta linear na faixa de concentração de 1,37 x 10-6 a 2,14 x 10-5 mol L-1, obtendo-se uma sensibilidade de 0,68 μmol L-1 e com limites de detecção (LD) e quantificação (LQ) iguais a 1,06 x 10-6 e 3,52 x 10-6 mol L-1. Estes valores estão próximos aos relatados na literatura para eletrodos modificados com nanopartículas metálicas. Por fim, a técnica de espectroscopia de impedância eletroquímica confirmou que a sequência de deposição, o número de bicamadas, bem como a natureza nanoestruturada dos filmes LbL afetam a resistência de transferência de carga. Portanto, a presença do AH na arquitetura do filme diminui a resistência de transferência de carga pelo fato desta macromolécula ser constituída por grande quantidade de grupos funcionais, os quais disponibilizam maior número de sítios para interações com o grupo piridínio do SiPy+Cl-, e consequentemente disponibilizam maior quantidade de Np-Pt na superfície do eletrodo.

The synthetic estrogen 17α-ethinylestradiol (EE2) is an endocrine disrupting chemical (EDC) of concern due to its persistent nature and widespread presence in the aquatic environment. In mammals, effects of developmental EDC exposure on reproduction and behavior not only persist to adulthood after discontinued exposure, but are also inherited by several consecutive unexposed generations. The results presented in this thesis demonstrate that non-reproductive behavior in fish is highly sensitive to the influence of EE2 during development and the effects do not appear to be restored after a long recovery period in clean water. We have shown that exposure to low doses of EE2 during development results in increased anxiety in two fish species (zebrafish and guppy) and their offspring. We have also demonstrated that the effects of EE2 on anxiety are apparent in both sexes and are transgenerationally transmitted to two consecutive generations of unexposed offspring in the guppy. In order to investigate the possible biological mechanisms of the observed persistent effects on non-reproductive behavior, we also performed an RNA sequencing analysis of the whole-brain transcriptome in developmentally exposed zebrafish after remediation in clean water until adulthood. Differential expression of 33 genes in males and 62 genes in females were observed as a result of EE2 exposure, with only one gene affected in both sexes. Functional analysis revealed cholesterol biosynthesis and circadian rhythm to be the top two affected pathways in males and females, respectively. Both pathways have previously been implicated in anxiety behavior and represent possible candidates connecting the transcriptome alterations to the observed behavioral phenotype. The study represents an initial survey of the fish brain transcriptome by means of RNA sequencing after long-term recovery from developmental exposure to an estrogenic compound.

In this thesis, we have analysed the effects of EE2 on non-reproductive behaviours and fertility. We have showed that two doses of EE2 in male adult short-term exposures evokes opposite behaviours in the novel tank test. A lower dose induced increased bottom-dwelling, a sign of increased anxiety and a higher dose increased surface-dwelling, which would likely expose themselves to predation in a natural environment. Increased shoaling was observed in both exposures, possibly affecting feeding and reproduction opportunities. Fertility analysis of these fish demonstrated a complete inhibition of spawning in the highest dose group. To investigate mechanisms behind the spawning failure, we examined expression levels of genes involved in zebrafish sex differentiation and maintenance of gonadal function. We found downregulated transcription levels of male-predominant genes, suggesting a demasculinization of the testes contributing to functional sterility in these fish. We have demonstrated that non-reproductive behaviour in zebrafish is highly sensitive to EE2 exposure during development. After exposing male and female zebrafish to low doses of EE2 followed by remediation in clean water until adulthood, the fish displayed increased anxiety and shoaling behaviour, demonstrating persistent effects of EE2. Furthermore, behavioural effects were transferred to their progeny. Decreased fertilisation success of the developmentally exposed fish was observed in both sexes when mated to untreated animals of the opposite sex. These fertility effects persisted although the fish had a long remediation period, implying likely reduced fitness of fish populations in aquatic environments. Based on our findings on non-reproductive behaviours and fertility, we performed RNAsequencing analysis of the brain and testes in order to investigate possible biological mechanisms behind the persistent effects. There is a need for biomarkers allowing detection of both reversible and irreversible effects in animals exposed to estrogenic substances, hopefully contributing to better risk assessments for EDCs. Results from RNA-sequencing would serve as a basis for continued studies in pursuit of potential biomarkers.

17α-ethinylestradiol (EE2) is a synthetic hormone, derivative of the natural hormone estradiol. EE2 is one of the the most prescribed drugs in the world. It belongs to the estrogenic endocrine disrupter chemicals. These compounds are able to alter functions of the endocrine system and cause adverse effects in the organism, offspring and (sub)population. In this thesis, there are observed effects of 17α-ethinylestradiol on enzyme activities of main enzymes involved in phase I of xenobiotic biotransformation, i.e. cytochromes P450 (CYP), in vitro. Isoforms of CYP subfamilies 1A, 2B, 2C, 2E and 3A were studied in rats and humans. Each CYP isoform was incubated with EE2 at two concentrations, 10μM EE2 and the concentration corresponding to the substrate concentration in the specific marker reactions of individual CYP isoforms. The results indicate, that in rat liver microsomes the activity of all studied isoforms except CYP1A2 was decreased in the presence of EE2. When EE2 was added to the incubation mixture at the concentration of the reaction substrate, the greatest decrease in enzyme activity was observed for CYP2C6, with the remaining activity only 36%. In human liver microsomes, the activity of CYP2B6, CYP2C9, CYP2E1 and CYP3A4 was also effected by EE2. As in the case of rat model, CYP2C subfamily...

Exposure to exogenous estrogens such as synthetic 17α-ethinyl estradiol (EE) occurs via multiple sources (i.e. hormonal contraceptives, environmental contamination, hormone replacement therapy). The natural estrogen, 17β-estradiol (E2), is a well-studied immunomodulatory hormone at both environmental and pharmacologic levels. Conversely, little data exist regarding the immune effects of EE at either environmentally-relevant exposure levels or at pharmacological levels. Further, EE is delivered to patients in a clinical setting via different routes of exposure (e.g. subcutaneous or oral). Many key questions in relation to potential immunological effects of EE are unanswered. Important variables in estrogen-modulation of the immune system include: (i) dose, (ii) age, (iii) gender, and (iv) route of exposure. Thus, pertinent questions emerge. Does exposure to EE at low concentrations for a subacute duration affect the immune or reproductive systems? Are the effects similar in both hormones and between sexes? Are these effects similar in juvenile and aged mice? How do the effects compare across two common routes of exposure (subcutaneous versus oral)? To address these questions, three separate studies were performed. In the first study, we investigated whether very low, but environmentally relevant, doses of EE, E2 (10 ng/kg body weight), or vehicle orally administered every other day for 21 days to young (6 week-old) and aged (>15 month-old) C57BL/6 mice had immunomodulatory effects. As expected, significant gender and age-related differences were noted with regard to thymus weight, thymocyte recovery, spleen weight, and splenocyte recovery. However, low dose treatment of either E2 or EE had no marked effects on the thymus or spleen organ to body weight ratios, cell numbers, or lymphocyte subsets. Low dose oral estrogens did not alter the ability of activated splenocytes to induce interferon-γ or nitric oxide. No effects on male reproductive organ to BW ratios of young or aged mice were found. Similarly, with the exception of E2-stimulating effects on the female reproductive tract of young mice, there were no pronounced effects in females. In separate studies, intact juvenile female and male C57BL/6 mice were given daily subcutaneous (second study) or oral (third study) doses of either EE or E2 (0.04, 0.4, or 4.0 μg per 25 g BW) for 21 days. In the subcutaneous exposure study, both EE and E2 morphologically altered uterine and seminal vesicle weights. However, EE had a more pronounced effect compared to E2, especially in males, even at the lowest dose administered. Additionally, like E2, EE induced thymic atrophy in both sexes. In female mice, thymic atrophy and thymic cellularity were significantly decreased by subcutaneous EE and E2 at doses of 0.4 and 4.0 μg/25 g body weights. EE elicited significantly more pronounced thymic atrophy-inducing effects compared to E2 at the 4.0 μg/25g dose. In males, thymocyte cellularity was decreased by both subcutaneous EE and E2 only at the highest dose tested (4.0 μg/25 g body weight), whereas only 4.0 EE significantly decreased thymus to body weight ratios. Neither splenic weights, splenic cellularity, nor splenic cell phenotype were affected by either estrogenic compound regardless of route of exposure. Oral exposure of EE or E2 did not induce marked immunological effects. Collectively, these data demonstrate that select thymic and reproductive endpoints are significantly altered following a 21-day subcutaneous exposure to either EE or E2 and that the thymus is a more sensitive target than the spleen with regard to subacute exposure to EE. In addition, EE at a comparable dose was more potent than E2 at exerting thymic and reproductive organ morphological alterations. Furthermore, route of administration is critical, as subcutaneous exposure induced far more dramatic thymic and reproductive morphological alterations than did oral administration. Future studies need to address the precise mechanism through which EE induces thymic atrophy and diminished thymus cellularity. Are these effects mediated directly through the thymus, perhaps through estrogen-induced increased thymocyte apoptosis or alterations to thymic epithelial cells? Or could EE be mediating alterations via bone marrow stem cells targeted for distribution to the thymus? Our novel findings regarding EE-induced effects on the thymus are of health significance and set the stage for future work. / Master of Science

Made available in DSpace on 2017-07-20T13:41:56Z (GMT). No. of bitstreams: 1 Vitor da Silveira Freitas.pdf: 1933649 bytes, checksum: a5cfbb4c538352e89ea78bce140383ec (MD5) Previous issue date: 2015-02-03 / Endocrine disrupters (EDs) are substances that simulate, mimic or block the action of natural hormones in humans and other animals. Its presence in surface water and wastewater generates harmful effects that is proven in some fish species, but studies about effects in humans are still controversial. Among the EDs is the 17α-ethinylestradiol (EE2), a synthetic hormone used contraceptives and hormone replacement treatments. This work evaluated the removal of EE2 in water prepared in laboratory, by the conventional treatment in bench scale (CT), CT with addition of powdered activated carbon (CT + PAC) and CT with a subsequent step of heterogeneous photocatalysis using TiO2 (CT + TiO2). The study water was prepared by adding kaolin to raise the turbidity up to 100 ± 10 NTU and, EE2 to a final concentration of 40 mg L-1. The CT was constituited by coagulation using aluminum sulfate (12 mg L-1), followed by flocculation, sedimentation and filtration. The CT + PAC differed by the addition of powdered activated carbon at concentrations of 5 mg L-1 and 7.5 mg L-1 before the coagulation step. The CT + TiO2 step was made of the way after the completion of the CT, 1 L of sample was stored and treated by the heterogeneous photocatalysis. The CT showed removal of EE2 41,75% and 44,33%. The treatment that added activated carbon proved to be more effective removing EE2 (59.63% and 62.25%), and the removal percentage increased with increasing the concentration of powdered activated carbon. The CT + TiO2 also proved an effective treatment, removing 52,5 to 56,4% of EE2. / Interferentes endócrinos (IEs) são substâncias que simulam, bloqueiam ou memetizam a ação de hormônios naturais em humanos e outros animais. Sua presença em águas superficiais e residuárias gera efeitos nocivos já comprovados em espécies de peixes, porém estudos sobre efeitos causados em seres humanos ainda são controversos. Entre os IEs, está o 17α-etinilestradiol (EE2), hormônio sintético utilizado em pílulas anticoncepcionais e tratamentos de reposição hormonal. Neste trabalho foi avaliada a remoção do EE2 em água preparada para estudo utilizando tratamento convencional (TC), TC com adição de carvão ativado em pó (TC + CAP) e TC com posterior etapa de fotocatálise heterogênea utilizando TiO2 (TC + TiO2). Os ensaios foram realizados em equipamento de jarteste, com sulfato de alumínio como coagulante. A água de estudo foi preparada adicionando-se caulinita para elevar a turbidez até 100 ± 10 uT e EE2 (Sigma-Aldrich®) até concentração final de 40 mg L-1. O TC foi constituído de coagulação com dosagem de sulfato de alumínio de 12 mg L-1 seguida de floculação, sedimentação e filtração. O TC + CA diferenciou-se pela adição de carvão ativado em pó nas concentrações de 5 mg L-1 e 7,5 mg L-1 antes da etapa de coagulação. O TC + TiO2 foi realizado com 1 L de amostra após TC, a qual foi armazenada e efetuada a etapa de fotocatálise heterogênea. O TC apresentou remoção de EE2, na ordem de 41,8% e 44,3%. O TC + CAP apresentou melhor eficiência de remoção do EE2 (59,6% e 62,3%), e sua porcentagem de remoção aumentou com aumento da concentração de carvão ativado em pó. Com TC + TiO2 obteve-se eficiência de remoção de EE2 de 52,5 a 56,4% nos ensaios realizados.