Obesity and the metabolic complications associated with it are increasing globally. Sedentary lifestyles, poor diet and genetic predisposition contribute to obesity. In addition, environmental chemicals such as Bisphenol A (BPA) may play a significant role. Exposure to BPA has been correlated with an array of adverse health effects on the endocrine system and whole-body homeostasis. This has resulted in manufacturers replacing it with structural analogues such as Tetra Methyl Bisphenol F (TMBPF), Bisphenol F (BPF), Bisphenol AP (BPAP), and fluorine-9-bisphenol (BHPF). BPA is a suspected obesogen as it can induce adipogenesis in human and murine preadipocytes. The effects of the BPA analogues listed above on adipogenesis have yet to be evaluated. The aim of this project is to investigate their adipogenic effects. For this purpose, we used 3T3-L1 mouse embryonic fibroblasts. This cell model can be differentiated into mature adipocytes with appropriate inducers including 3-isobutyl-1-methylxanthine (IBMX), insulin and dexamethasone, a synthetic steroid. To assess the effects of BPA analogues, the cells were treated with varying concentrations of TMBPF, BPF, BHPF, BPA, or BPAP in place of dexamethasone. The expression levels of mature adipocyte markers were assessed at mRNA and protein levels to determine the adipogenic potential of the analogues. Lipid accumulation was evaluated by Nile Red staining. A time course was performed to assess the expression levels of known transcriptional regulators of adipogenesis. The results indicate that TMBPF, BPF and BPA increase 3T3-L1 adipogenesis. BHPF and BPAP did not affect adipogenesis in this model. BPF appears to be at least as good as BPA at inducing adipogenesis. TMBPF, on the other hand, can induce adipogenesis to a greater extent than the other chemicals, including BPA, as evidenced by increased expression of adipogenic markers and lipid accumulation. Finally, key transcription factors C/ebpδ and C/ebpα, part of the adipogenic transcriptional cascade, were up-regulated at III two and six hours post-treatment by TMBPF. BPA also up-regulated C/ebpδ at two hours post-treatment. Though the adipogenic effects have become apparent for some of these analogues, the mechanism by which they elicit their effects remains to be discovered. More research is required to deduce the mechanism of action and to provide consensus on what the effects of these replacement bisphenols actually are.

Les activités d'élevage sont responsables de la dissémination dans l'environnement d'un grand nombre de polluants, dont les perturbateurs endocriniens (PE) qui affectent le système endocrinien des organismes vivants. La disruption endocrinienne se fait par la liaison des PE sur des récepteurs nucléaires spécifiques dont le récepteur aux strogènes ERα, le récepteur à la dioxine AhR, le récepteur X aux pregnanes PXR, le récepteur aux androgènes AR et le récepteur régulant la prolifération des peroxysomes, PPARγ. Les hormones stéroïdes sont particulièrement actives sur le récepteur ERα. Elles sont naturellement produites par les animaux et concentrées dans les effluents d'élevage épandus sur les sols agricoles. Ce travail de thèse s'est focalisé sur l'étude du devenir des hormones dans des systèmes de gestion des lisiers porcins, à échelle réelle ou contrôliée, en conditions anaérobies ou aérobies. Au préalable, la méthodologie pour l'analyse des hormones dans le lisier a été validée. Les résultats montrent que les hormones sont principalement contenues dans la fraction solide; dans cette fraction les mesures d'activité strogénique (ERα) ont révélé une activité non explicable par les concentrations en hormones, suggérant la présence d'autres composés ayant une activité sur ERα. La quantification des nonylphénols, actifs sur ERα n'a pas permis d'expliquer cette activité. L'étude d'autres voies de perturbation endocrinienne via l'activation des récepteurs AhR, PXR, PPARγ et AR a permis de détecter une forte activité sur le récepteur AhR. L'analyse chimique de cette fraction a montré l'absence de dioxines et d'hydrocarbures aromatiques polycycliques, suggérant l'implication d'autres PE qui restent à être identifiés. Dans les systèmes de traitement sous conditions réelles ou contrôlées, les conditions aérobies sont plus efficaces pour éliminer les hormones et les activités strogéniques et « dioxin-like » associées, bien que cette dernière semble plus récalcitrante. / Livestock activities are responsible for the release of a wide range of pollutants in the environment. Among these pollutants, the endocrine disruptors (ED) can affect the endocrine functions of living organism. The endocrine disruption occurs via the binding of ED to specific nuclear receptors such as the estrogen receptor ERα, dioxin receptor AhR, pregnane-X-receptor (xenobiotics), androgen receptor AR and peroxysome proliferator-activated receptor γ, PPARγ. Steroid hormones are particularly active on ERα receptor. Animals naturally produce high amounts of hormones which are concentrated in manure used for land spreading. This study deals with the fate of hormones in swine waste management facilities at full or pilot scale, under both anaerobic and aerobic conditions. Firstly, the analysis of hormones in such a complex matrix was validated. Hormones are mainly present in the solid fraction of the manure. At the same time, estrogenic activity measurements showed that in this solid fraction, the estrogenic activity cannot be explained by hormones; which suggest the presence of other compounds active on ERα. Nonylphenols concentrations cannot explain this additional activity. The study of the other pathways of endocrine disruption through the activation of AhR, PXR, PPARγ, and AR allowed to measure high AhR activity in the solid fraction of manure. The chemical analysis of this fraction did not show the presence of dioxins and polycyclic aromatic hydrocarbons traditionally involved in such kind of activity; it suggests the presence of other AhR ligands that remain to be identified. In swine manure treatment systems, aerobic conditions were more efficient to remove hormones and the associated estrogenic and AhR activities, even if this last seemed to be more recalcitrant.

[pt] As bifenilas policloradas e os éteres difenílicos polibromados constituem duas classes de poluentes orgânicos persistentes (POPs), altamente lipofílicos, capazes de resistir à biodegradação e bioacumular através da cadeia alimentar. Os PCBs foram utilizados principalmente como fluidos isolantes em capacitores e transformadores, bem como em diversos equipamentos elétricos. Os PBDEs são retardantes de chamas, os quais são aplicados em computadores, televisores e aparelhos elétricos e eletrônicos em geral. As altas concentrações destes poluentes no meio ambiente ocorrem por diversos fatores, dentre os quais podemos citar o descarte de equipamentos eletrônicos obsoletos. Ambos os poluentes são interferentes endócrinos, provocam alterações reprodutivas, possuem efeitos carcinogênicos e são neurotóxicos. Os seres humanos, por ocuparem o topo da cadeia alimentar, estão sujeitos a elevado risco de contaminação por estes compostos. No presente estudo, foram determinados os níveis de PCBs e PBDEs em diferentes espécies de peixes oriundos da Baía da Ilha Grande, localizada ao Sul do Estado do Rio de Janeiro, Brasil. Os PCBs foram os poluentes predominantes e os níveis de PBDEs estão abaixo do limite de quantificação. Os PCBs foram encontrados em três espécies de peixes e as concentrações variaram entre 2,29 e 27,60 ng g(-1) em peso úmido para amostras de músculos e entre 3,41 e 34,22 ng g(-1) também em peso úmido para amostras de fígados. O PCB-87 foi o congênere dominante, onde sua concentração média foi de 34,22 ng g(-1) em peso úmido nas amostras de corvinas. Foram estabelecidas correlações entre as concentrações de PCBs e variáveis biométricas dos indivíduos, tais como comprimento, peso e teor lipídico, bem como a diferenciação estatística em função da sazonalidade. / [en] Polychlorinated biphenyls (PCBs) and Polybrominated Diphenyls Ethers (PBDEs) are two highly lipophilic classes of persistent organic pollutants (POPs) able to resist degradation and with the ability to bioaccumulate through the food chain. PCBs were primarily used as insulating fluids in capacitors and transformers, as well as in several electrical equipments. The high levels of these pollutants in the environment can occur due to several factors, among which the disposal of obsolete electronic equipment. Both pollutants are endocrine disrupters that can cause reproductive alterations. They are neurotoxic and have carcinogenic effects. Humans, by occupying the top of food chain, are subject to a high risk of contamination by these compounds. In this study, we determined the levels of PBDEs and PCBs in different fish species from the Ilha Grande Bay, located in the southern state of Rio de Janeiro, Brazil. PCBs were the predominant pollutants and PBDEs levels were below the limit of quantification. PCBs concentrations were found in the different tissues of fish at concentrations ranging from 2.29 to 27.60 ng g(-1) wet wt in muscles and from 3.41 to 34.22 ng g(-1) wet wt in livers. PCB-87 was the major congener detected, with a mean concentration of 34.22 ng g(-1) wet wt in croaker samples. Correlations were established between the concentration of PCBs and biometric variables of the fish individuals, such as length and fat content, and a statistical variation due seasonality was also observed.

Endocrine disruptors are natural or manmade substances which affect hormonal systems of organisms. Biologically relevant concentrations are commonly being detected in the environment. The effluents of wastewater treatment plant present their significant secondary source. Due to their occurence and quantity the interest in mixtures increases. Ecotoxicological assays with genetically modified Saccharomyces cerevisiae were aplied to verify reliability of predictive mathematical models for mixtures of standards (estrone, 17β-estradiol, 17α-ethinylestradiol, estriol, bisphenol A, irgasan, 4-nonylphenol). Chromatographic analysis along with yeast assays were used for the evaluation of real samples of wastewater treatment plant effluents and sediments. Schindler's predictive model and Full logistic model (FLM) were more reliable for predicting the whole dose-response curve compared to Generalized concentration addition (GCA). Predicted values of a parameter EC50 from all three models were comparable to empirical measurements. Three out of four samples exhibited estrogenic activity 0.65 - 1.70 ng/L 17β-estradiol ekvivalent (EEQ) above the limit of detection 0.13 - 0.33 ng/L EEQ. Antiestrogenic activity was detected in one of the samples. Prediction could be carried out only in the case of the sediments...

A poluição marinha por petróleo e seus derivados é uma preocupação crescente de caráter global. O litoral norte do estado de São Paulo é hoje caracterizado como a região mais altamente impactada por esses contaminantes de toda a costa Sul e Sudeste do país. Dentre as substâncias que compõem esses produtos estão os Hidrocarbonetos Aromáticos Policíclicos (HPAs), como o fenantreno, que apresentam potencial de alterar o sistema endócrino de peixes, gerando desajustes hormonais de alto risco para o processo reprodutivo dos animais expostos. Com base nestes fatos, o presente trabalho buscou verificar efeitos do fenantreno como desregulador endócrino em juvenis de E. marginatus. Essa espécie se caracteriza pelo hermafroditismo protogínico, de modo que os juvenis costumam apresentar altas concentrações de esteroides gonadais, o que gera preocupação quanto os efeitos reprodutivos decorrentes de alterações no padrão de produção de esteroides, especialmente em uma espécie que já vem sofrendo declínios populacionais por conta da sobrepesca. A CL50 encontrada para juvenis de E. marginatus foi 1,51 mg⁄L. Em seguida, foi realizado um bioensaio subletal (96h) com quatro grupos experimentais (n=5) em duplicata: grupo controle; duas concentrações distintas de fenantreno (0,1 mg⁄L e 1 mg⁄L) e grupo exposto ao veículo de diluição (0,004% de etanol). Foram dosadas as concentrações de 17β-estradiol (E2), testosterona (T) e 11-cetotestosterona (11-KT) plasmáticos por ELISA. Gônadas, fígado e baço foram processados para análise histológica. Foi conduzido bioensaio in vitro com incubação de fragmentos gonadais sob ação de fenantreno (50μM) ou etanol. Os níveis dos mesmos esteroides também foram dosados por ELISA. A exposição in vivo ao fenantreno resultou em aumento na área dos hepatócitos, bem como no número de centro melanomacrofágicos e hemossiderose no baço. O etanol induziu efeitos similares no baço. Os níveis de E2 e T não se alteraram no plasma ou no meio de incubação in vitro. O fenantreno reduziu a concentração de 11-KT in vitro e in vivo. No plasma, o etanol também causou esse decréscimo. Considerando a importância do 11-KT no desenvolvimento dos ovários em teleósteos, o fenantreno parece causar desregulação da esteroidogênese em juvenis de E. marginatus, possivelmente gerando disfunções durante a inversão sexual / Marine pollution by crude oil and its residual products is a growing global concern. The Northern coast of São Paulo is characterized as the highly impacted area by these contaminants through Brazil\'s South and Southeast coast. Polycyclic aromatic hydrocarbons (PAH), such as phenanthrene, are the main crude oil components and have a significant toxic potential to biota, acting as endocrine disruptors (ED) and negatively impacting reproduction. This study aimed to investigate the effects of phenanthrene as ED on gonadal steroidogenesis in E. marginatus juveniles. As a hermaphrodite protogynous species, E. marginatus juveniles maintain high levels of plasma steroids as substrates for sex inversion, which causes concern about reproductive effects of disruptions in steroid production patterns, especially in an overfished species. LD50 to E. marginatus exposed to phenanthrene was established in 1.51 mg⁄L. An in vivo sublethal exposure (96 h) to phenanthrene was carried out at two concentrations (0.1mg⁄L and 1 mg⁄L); exposure to the vehicle (ethanol) was also performed. Plasma levels of 17β-estradiol (E2), testosterone (T) and 11-ketotestosterone (11-KT) were measured by ELISA. Gonads, liver and spleen were processed for histological analysis. In an in vitro bioassay, gonad fragments were incubated with phenanthrene (50μM) or ethanol. Steroid levels in the culture media were also measured by ELISA. The in vivo exposure to phenanthrene triggered an increase of the area of the hepatocytes, increased number of melanomacrophagic centers and hemosiderosis in the spleen. Ethanol also induced similar effects on spleen. E2 and T levels did not change neither in plasma nor in vitro media. Phenanthrene sharply reduced 11-KT levels in vitro and in vivo. In plasma, ethanol also decreased 11-KT levels. Considering the importance of 11-KT in fish developing ovaries, phenanthrene seems to disrupt steroidogenesis in juvenile grouper, possibly being able to cause dysfunctions during sex change

O objetivo deste trabalho foi avaliar a liberação de Bisfenol A (BPA) de sistemas adesivos resinosos ortodônticos in vitro e in vivo. No estudo in vitro foram testadas 5 marcas comerciais de sistemas adesivos resinosos ortodônticos (Eagle Spectrum, Enlight, Light Bond, Mono Lok II e Transbond XT). Por meio da simulação de exposição intraoral, os corpos de prova foram imersos numa solução água/etanol e a liberação de BPA foi medida nos tempos de 30 minutos, 24 horas, 1 dia, 1 semana e 1 mês. No estudo in vivo utilizou-se amostra composta por 20 pacientes com indicação para tratamento ortodôntico com aparelhos fixos. Foram coletadas amostras de saliva em 5 tempos: antes, 30 minutos, 24 horas, 1 dia, 1 semana e 1 mês após a colagem dos bráquetes e as de urina em 4 tempos: antes, 1 dia, 1 semana e 1 mês após a colagem. Todos os compósitos avaliados liberaram pequena quantidade de BPA, sendo que o compósito Enlight-ORMCOR foi o que apresentou maior liberação,1020 ng/g no tempo de 1 mês. Os maiores níveis de BPA na saliva, foram encontrados no tempo de 30 minutos (1,0445 ng/mL) e na urina, 24 horas (5,035 ng/mL) após a colagem dos bráquetes. Mesmo que as quantidades de BPA liberadas fossem pequenas, houve diferença significativa quando esses valores foram comparados com os níveis iniciais, sugerindo aumento da quantidade de BPA no organismo com a colagem dos bráquetes ortodônticos. Como a literatura especializada têm destacado os potenciais tóxicos do BPA e têm sugerido alterações celulares \"com baixas\" doses, mais estudos são necessários para se chegar a um consenso no sentido de propiciar segurança no uso desses materiais. / The purpose of this study was measure the release of Bisphenol A (BPA) from the orthodontic resinous adhesive systems in vitro and in vivo. The study was divided into two stages: At in vitro study, five trademarks of Resinous Adhesive Systems (Eagle Spectrum, Enlight, Light Bond, Mono Lok II and Transbond XT) was tested. The samples were immersed in a water/ethanol solution simulating the intraoral exposition and the release of BPA was measured at times of 30 minutes, 24 hours, 1 day, 1 week and 1 month. At in vivo study, 20 patients with indication to fixed orthodontic appliances were used. Samples of saliva and urine were collected in these patients at previously determined time. To the saliva, it was collected 5 times ( before bonding the orthodontic brackets and 30 minutes, 24 hours, 1 day, 1 week and 1 month after this procedure); to the urine, it was collected 4 times ( before, 1 day, 1 week, 1 month, after bonding the orthodontic brackets). All the tested resinous adhesives released a small quantity of BPA, with peack at 1 month, with Enlight resinous presenting the highest level (1020 ng/g). The peack level in saliva (130445 ng/ml) and urine (5.035 ng/ml) were found in 30 minutes and 24 hours after the bonding of fixed appliances, respectively. However the quantities of released BPA are small which validate the security of the procedure. A significant difference was observed when these values were compared to the initial levels, suggesting a correlation of the increase of the quantity of BPA in the body and the bonding of the orthodontic appliances. As several studies have reported, the probable toxic effect of BPA and cellular changes in \"low doses\", more studies are necessary to reach a consensus. to provide security in the use of such materials.

O objetivo deste trabalho foi avaliar a liberação de Bisfenol A (BPA) de sistemas adesivos resinosos ortodônticos in vitro e in vivo. No estudo in vitro foram testadas 5 marcas comerciais de sistemas adesivos resinosos ortodônticos (Eagle Spectrum, Enlight, Light Bond, Mono Lok II e Transbond XT). Por meio da simulação de exposição intraoral, os corpos de prova foram imersos numa solução água/etanol e a liberação de BPA foi medida nos tempos de 30 minutos, 24 horas, 1 dia, 1 semana e 1 mês. No estudo in vivo utilizou-se amostra composta por 20 pacientes com indicação para tratamento ortodôntico com aparelhos fixos. Foram coletadas amostras de saliva em 5 tempos: antes, 30 minutos, 24 horas, 1 dia, 1 semana e 1 mês após a colagem dos bráquetes e as de urina em 4 tempos: antes, 1 dia, 1 semana e 1 mês após a colagem. Todos os compósitos avaliados liberaram pequena quantidade de BPA, sendo que o compósito Enlight-ORMCOR foi o que apresentou maior liberação,1020 ng/g no tempo de 1 mês. Os maiores níveis de BPA na saliva, foram encontrados no tempo de 30 minutos (1,0445 ng/mL) e na urina, 24 horas (5,035 ng/mL) após a colagem dos bráquetes. Mesmo que as quantidades de BPA liberadas fossem pequenas, houve diferença significativa quando esses valores foram comparados com os níveis iniciais, sugerindo aumento da quantidade de BPA no organismo com a colagem dos bráquetes ortodônticos. Como a literatura especializada têm destacado os potenciais tóxicos do BPA e têm sugerido alterações celulares \"com baixas\" doses, mais estudos são necessários para se chegar a um consenso no sentido de propiciar segurança no uso desses materiais. / The purpose of this study was measure the release of Bisphenol A (BPA) from the orthodontic resinous adhesive systems in vitro and in vivo. The study was divided into two stages: At in vitro study, five trademarks of Resinous Adhesive Systems (Eagle Spectrum, Enlight, Light Bond, Mono Lok II and Transbond XT) was tested. The samples were immersed in a water/ethanol solution simulating the intraoral exposition and the release of BPA was measured at times of 30 minutes, 24 hours, 1 day, 1 week and 1 month. At in vivo study, 20 patients with indication to fixed orthodontic appliances were used. Samples of saliva and urine were collected in these patients at previously determined time. To the saliva, it was collected 5 times ( before bonding the orthodontic brackets and 30 minutes, 24 hours, 1 day, 1 week and 1 month after this procedure); to the urine, it was collected 4 times ( before, 1 day, 1 week, 1 month, after bonding the orthodontic brackets). All the tested resinous adhesives released a small quantity of BPA, with peack at 1 month, with Enlight resinous presenting the highest level (1020 ng/g). The peack level in saliva (130445 ng/ml) and urine (5.035 ng/ml) were found in 30 minutes and 24 hours after the bonding of fixed appliances, respectively. However the quantities of released BPA are small which validate the security of the procedure. A significant difference was observed when these values were compared to the initial levels, suggesting a correlation of the increase of the quantity of BPA in the body and the bonding of the orthodontic appliances. As several studies have reported, the probable toxic effect of BPA and cellular changes in \"low doses\", more studies are necessary to reach a consensus. to provide security in the use of such materials.

Les phtalates (PAEs) sont un groupe de contaminants organiques émergents qui sont devenus une préoccupation majeure en raison de leur omniprésence dans le milieu marin et de leurs effets perturbateurs sur le système endocrinien. Cependant, leur répartition en Méditerranée est assez mal connue, principalement en raison des difficultés analytiques et du risque élevé de contamination des échantillons lors du processus analytique. En outre, les débris de plastique en milieu marin contiennent des additifs comme les PAEs, qui sont ajoutés lors de l’étape de fabrication du plastique. Dans la première partie de cette thèse, une méthode analytique a été optimisée et validée pour la détermination de 8 PAEs à l'état de traces en milieu marin. Brièvement, 1L d'échantillon filtré est passé à travers des cartouches de verre contenant 200 mg d'Oasis HLB, puis élué à l’aide de 6mL d'acétate d'éthyle. Notre méthode donne des rendements d’extraction compris entre 95 et 115 % et des blancs acceptables. Dans un second temps, un suivi annuel de la contamination de la Baie de Marseille a été effectué de décembre 2013 à novembre 2014. Les résultats ont montré la présence de 7 PAEs, avec des concentrations totales variant de 130 à 1330 ng L-1. Dans la dernière partie de cette thèse, deux échantillons de plastique communs (sac de poubelle et gaine de câble électrique) ont été incubés dans de l'eau de mer naturelle dans des conditions contrôlées de laboratoire, de manière à évaluer la migration de PAEs depuis ces matériaux en fonction de différentes conditions environnementales comme la température, la présence de lumière, ou encore la présence de bactéries. / Phthalic Acid Esters (PAEs) are a group of emerging organic contaminants that have become a serious issue because of their ubiquitous presence on the marine environment worldwide and for the endocrine disrupting effects in animals and humans. However, little is known about their distribution in the Ocean, mainly because of analytical difficulties and the high possibility of ambient sample contamination. Plastic debris in marine environment includes resin pellets, macro- and microplastic fragments, and contains additives such as PAEs that might be released in the aquatic environment in unknown proportion. In our work, we improved an analytical method for the determination of 8 PAEs, at trace levels in marine and fresh waters. In the first part of the thesis, the method was validated for different seawater salinities and wastewater treatment plant outlet. By passing 1 L of sample through glass cartridges packed with 200 mg of Oasis HLB and eluted with 6 mL of ethyl acetate, the recoveries of 8 PAEs ranged from 95 to 115 % with acceptable blank values (below 0.4-4.0 % of the masses measured in different seawater samples). In a second part, PAE distribution in the Marseille Bay has been evaluated though a one-year monitoring from December 2013 to November 2014. The results showed the occurrence of six PAEs with total concentrations ranging from 130 to 1330 ng L-1. In the last part of this thesis, two common plastic samples as trash plastic bags and insulation layer of electric cables were incubated in natural seawater in laboratory conditions and studied for the release of PAE. Release ws observed for the different PAEs with kinetics varying according to the plastic type.

Há evidências crescentes de que os desreguladores endócrinos (DE) podem afetar negativamente os seres humanos. Águas superficiais e subterrâneas são as principais fontes de obter a sua potabilidade, no entanto, podem ser contaminadas por DE, que não são totalmente removidos pelos processos convencionais de tratamento de água e esgoto. Alguns problemas de saúde estão relacionados à exposição dos seres humanos aos DE, sendo a obesidade um deles. Atualmente vive-se um aumento da prevalência da obesidade em todo o mundo, fato considerado preocupante, considerando-se seu potencial impacto no sistema de saúde, pois, as principais doenças crônicas como diabetes e doenças cardiovasculares, tem a obesidade como grande fator de risco. Por meio de revisão de literatura, este artigo buscou reunir publicações científicas relacionando a exposição aos DE com a obesidade, com o objetivo de verificar a importância de sua remoção dos corpos hídricos, preservando a saúde da população e da biota aquática. A maioria dos estudos selecionados sugere associação entre DE e obesidade em humanos. / There is growing evidence that endocrine disrupters (ED) may adversely affect humans. Surface and ground water are the main sources to get their potability however, can be contaminated by ED, which are not completely removed by conventional processes of water and sewage treatment. Some health problems are related to the exposure of humans to ED, obesity being one of them. Currently lives an increase in obesity prevalence worldwide, a fact considered worrying, considering its potential impact on the health care system, for major chronic diseases like diabetes and cardiovascular diseases have obesity as a major risk factor. Through literature review, this paper aims to gather scientific publications relating to exposure to ED with obesity, in order to verify the importance of their removal from water bodies, preserving the population\'s health and aquatic biota. Most of the selected studies suggest an association between ED and obesity in humans.

Uma questão ambiental preocupante é a contaminação do meio ambiente por substâncias que interagem com os sistemas endócrinos de seres humanos e animais. Tais substâncias são denominadas desreguladores endócrinos e, como outros poluentes ambientais, apresentam uma variedade de fontes e grande potencial agressor à saúde humana. Neste trabalho, buscamos a aplicação de técnicas de espectroscopia vibracional e técnicas eletroquímicas ao estudo de desreguladores endócrinos, em termos de sua detecção, caracterização, estudo de sua reatividade, desenvolvimento de métodos para sua degradação fotoquímica, estudo dos mecanismos envolvidos e características dos produtos de degradação. O enfoque é voltado ao uso de técnicas espectroscópicas, com especial destaque para o desenvolvimento de metodologias de espectroscopia vibracional intensificadas, associadas ou não a sistemas eletroquímicos. Dentre os compostos considerados desreguladores endócrinos, o nosso trabalho é dedicado ao estudo fotoquímico e espectroeletroquímico das seguintes substâncias: o difenilalcano bisfenol A (BPA), os herbicidas triazínicos ametrina e atrazina, e os compostos organoclorados ácido 2,4-diclorofenoxiacético (2,4-D) e 2,4-diclorofenol (2,4-DCF). O estudo de processos de fotólise e degradação fotocatalítica mediada por TiO2 foram realizados para o BPA e para a ametrina. Tais processos mostram-se importantes para a remoção destes compostos do meio ambiente. Os estudos fotocatalíticos foram estendidos ainda para o uso de compósitos TiO2-Pr como catalisadores. Foi observado que a dopagem do TiO2 pelo íon terra rara praseodímio resulta em alterações nas propriedades físico-químicas do material semicondutor, sendo um método valioso para o aumento da atividade fotocatalítica do TiO2. Conclui-se ainda pela necessidade do controle da porcentagem de modificação química para a otimização do processo fotocatalítico, sendo a proporção de 1% praseodímio considerada ótima. O estudo de processos de fotólise e degradação fotocatalítica do BPA mediado por TiO2 mostra diferenças significativas entre o processo de degradação e mineralização, relacionadas à formação de intermediários orgânicos recalcitrantes. Para a ametrina observa-se que a fotólise e a fotocatálise envolvem mecanismos de degradação distintos. Estudos espectroeletroquímicos dos desreguladores endócrinos (DEC) foram conduzidos através de espectroscopia Raman intensificada (efeito SERS) visando a compreensão da natureza da interação química entre os adsorbatos e superfícies metálicas nanoestruturadas, bem como a caracterização vibracional dos produtos de processos faradáicos desses compostos sobre eletrodos. Produtos de reações químicas de oxidação e redução dos DEC foram identificados através de modificações espectrais em função de potenciais eletroquímicos anódicos e catódicos. / An environmental issue of concern is contamination of the environment by substances which interact with the endocrine systems of humans and animals. Such substances are called endocrine disruptors (ED) and, like other environmental pollutants, may produce adverse effects in human health. In this work, we explore the application of vibrational spectroscopy and electrochemical techniques in the study of ED, in terms of their detection, characterization, study of their reactivity, development of methods for their photochemical degradation, study of the involved mechanisms and characteristic of degradation products. The approach employs the use of advanced spectroscopic techniques, with special attention for the development of methodology of surface-enhanced vibrational spectroscopy, associated or not with electrochemical systems. Among the compounds thought to cause endocrine disruption, the present study is dedicated to the photochemical and electrochemical study of the following substances: the plasticizer bisphenol A (BPA), the triazinic pesticides ametrine and atrazine, and the organochlorine compounds 2,4-dichlorophenoxyacetic acid and 2,4-dichlorophenol. The study of photolytic and TiO2-mediated photocatalytic degradation was carried out for BPA and ametrine. Such processes are important for the removal of such substances from the environment. The photocatalytic studies were extended to include the use of TiO2-Pr composite as catalysts. The doping of TiO2 by the rare earth ion praseodymium results in changes in the physicochemical properties of semiconducting material, being a valuable method for enhancing the photocatalytic activity of TiO2. Our results showed the need of percentage control of the chemical modification for the optimization of the photocatalytic process, with the 1% praseodymium/titanium ration the optimal composition. The study of photolysis and TiO2-mediated photocatalytic degradation processes of BPA shows significant differences between the degradation and mineralization, suggesting the production of recalcitrant organic compounds. For ametrine, photolysis and photocatalytic degradation processes were found to occur via different mechanisms. Spectroelectrochemical studies of endocrine disruptors (ED) were carried out through surface-enhanced Raman spectroscopy (SERS effect) aiming at the understanding of the nature of the chemical interaction between these molecules and nanostructured metallic surfaces, and at the vibrational characterization of the products formed by faradaic charge transfer processes. Products of oxidation and reduction chemical reactions were identified through spectral changes observed in the SERS spectra as a function of cathodic and anodic potentials.