Aujourd'hui, les outils de lithographie utilisés dans l'industrie arrivent à leur limite de résolution en simple exposition. Pour continuer à diminuer les dimensions, il faut utiliser des techniques de double exposition, mais cela entraîne une explosion des coûts de fabrication. Cette thèse se focalise sur les aspects de modélisation de deux techniques, Sidewall Image Transfer et Directed Self-Assembly, qui sont pressenties pour permettre à l'industrie de continuer la réduction des dimensions des transistors, tout en minimisant les coûts. / Today, the lithographic tools used in industry came to their resolution limit in single patterning. In order to continue the reduction of dimensions, it is necessary to use double patterning, but this increase drastically the cost of manufacturing. This thesis focus on the modelisation aspects of two techniques, Sidewal Image Transfer and Directed Self-Assembly, that can help the industry continuing making transistors even smaller, while keeping the costs manageable.

Les anticorps anti-HLA d’isotype IgG sont une cause de perte de greffon en transplantation d’organes.Les tests « single antigen » (SAFB) sont les outils les plus précis et sensibles pour l’identification desanticorps anti-HLA dirigés contre le donneur (DSA) dans le sérum des receveurs. Leur résultat semiquantitatif,la MFI, n’est pas parfaitement associé à l’issue clinique, ce qui pourrait être dû à plusieursraisons. Premièrement, nous avons montré que les SAFB de classe I détectent fréquemment des anticorpsanti-HLA dénaturé de classe I, incapables de se lier à la surface cellulaire et donc n’ayant pas designification clinique, alors qu’ils ont un impact négatif sur l’accès à la transplantation. Leuridentification a été réalisée par un traitement acide des billes et par un SAFB modifié, les iBeads®.Ces deux tests montraient de bonnes fiabilité et concordance, mais le traitement acide pouvait parfoisêtre mis en défaut alors que les iBeads® auraient une sensibilité légèrement inférieure aux SAFBclassiques. Deuxièmement, nous avons déchiffré l’interférence liée au complément : les IgG anti-HLA de forte MFIsont capables d’activer le complément à la surface des billes, conduisant à une accumulation desproduits de dégradation du C4 et du C3, capables de réduire la détection des IgG anti-HLA. Nousavons également démontré que les IgM anti-HLA étaient capables d’interférer avec la détection desIgG à travers une compétition pour l’épitope, un encombrement stérique et une activation ducomplément. Troisièmement, nous avons montré que la détection des DSA avec les SAFB dans les éluats debiopsies de poumons transplantés, preuve formelle que ces DSA interagissent avec le greffon,constituait un facteur de risque de perte du greffon. Nous avons également développé un système decapture en résonance plasmonique de surface permettant de déterminer la concentration et l’affinitédes anticorps anti-HLA, ce qui pourrait permettre d’étudier la façon dont les DSA interagissent avec legreffon. / IgG HLA antibodies are a cause of graft loss in organ transplantation. The single antigen flow beadsassays (SAFB) are the most precise and sensitive assays to identify donor specific HLA antibodies(DSA) in recipient’s sera. Their semi-quantitative readout, the mean fluorescence intensity (MFI), is notperfectly associated with graft outcomes, which could be due to several factors.Firstly, we showed that class I SAFB frequently detects denatured class I HLA antibodies which areunable to bind cell surface and then are clinically irrelevant, while they actually impact the access to atransplant. Their identification was performed through SAFB acid-treatment and a modified SAFBassay, the iBeads®. They had a high reliability and a good concordance, but the acid-treatment assaycan be put at fault in a few cases whereas iBeads® appeared slightly less sensitive than classicalSAFB. Secondly, we deciphered the complement interference phenomenon: high MFI level IgG HLAantibodies activate the complement cascade at bead surface, leading to the deposition of C4 and C3degradation products which are able to reduce IgG HLA antibodies detection. We also demonstratedthat IgM HLA antibodies interfere with IgG detection through competition for the epitope, allosterichindrance and complement activation. Thirdly, we demonstrated that the detection of DSA with SAFB in lung biopsy eluates, proving that theDSA interact with the graft, was a risk factor for graft loss. We further developed a capture system insurface plasmon resonance allowing the concentration and affinity of HLA antibodies to bedetermined, which could allow the way that the DSA interact with the graft to be studied.

Abstract Computed tomography (CT) and interventional procedures cause relatively high patient doses compared with other imaging modalities in radiology. The optimization of the imaging equipment and procedures is important and necessary due to the known risks caused by ionization radiation. The different irradiation geometries and dose units between imaging techniques complicate the comparison of patients’ radiation exposure. Absorbed doses (D) of organs predict the tissue reactions of the procedures, while effective dose (E) is a useful means of comparing the stochastic effects of the different imaging procedures. A and E can be estimated from dosimetric measurements in a phantom. In vivo measurements are used during a radiological examination. In the present thesis, various properties of radiophotoluminescence dosimeters (RPLD) were investigated to verify the applicability of RPL dosimetry in radiology. The absorbed dose was determined in vaginal fornix of seven pregnant women, in the area near the head of the fetus during prophylactic catheterization before uterine artery embolization (UAE). The evaluation of the radiation exposure of digital subtraction angiography (DSA) and computed tomography angiography (CTA) was performed using an anthropomorphic phantom. Absorbed doses of organs and effective dose were determined for a typical four-vessel angiography of the cerebral area, including intracranial vessels, and for the cervicocerebral area, including both cervical and intracranial vessels. RPLD shows excellent dose linearity and minimal fading. The low dose detection threshold was determined to be 20 µGy with a coefficient of variation (CV) of 12.2%. The methodology is independent of photon energy in the energy range used in radiology. For seven patients studied, the mean value of D in vaginal fornix was 11.2 mGy (range 2.2–28.7) being low dose study when pulsed fluoroscopy with an optimized protocol is used without angiography exposures. In the assessment of cerebral vessels, the effective dose for CTA was approximately one-fifth of the dose compared with DSA. The dose for cervicocerebral vessels CTA was approximately one third higher compared with DSA. Conversion factors from the DAP and the DLP to the effective dose were calculated for the specific angiographic protocols. RPL dosimetry shows sufficient reliability in measuring radiation doses in radiology. / Tiivistelmä Tietokonetomografiakuvauksissa ja toimenpideradiologisissa tutkimuksissa potilaan säteilyaltistus on suhteellisesti korkeampi verrattuna muihin radiologisiin kuvausmenetelmiin. Kuvauslaitteiden erilaiset kuvausgeometriat ja annosyksiköt hankaloittavat potilaan säteilyaltistuksen vertailua eri tutkimusmenetelmien välillä. Kudokseen absorboituneen annoksen (D) avulla arvioidaan ionisoivan säteilyn suoraa haittavaikutusta kudokselle, kun taas efektiivisen annoksen (E) määrittämisellä arvioidaan säteilyn satunnaista haittaa. D ja E voidaan mitata annosmittarilla käyttäen potilasvastinetta. In vivo mittauksella saadaan annostietoa tutkimuksen aikana suoraan potilaasta. Radiofotoluminesenssiannosmittarin (RPLD) soveltuvuus radiologisiin annosmittauksiin varmistettiin tutkimalla mittarin eri fysikaalisia ominaisuuksia. RPLD:a käytettiin intravaginaalisen annoksen mittauksessa seitsemällä raskaana olevalla naisella. Potilaille tehtiin massiivisen verenvuodon ehkäisemiseksi kohdun valtimosuonten katetrointi läpivalaisuohjattuna ennen kohtuvaltimoiden tukkimishoitoa (UAE). Mittaustulokset antavat tietoa kudokseen absorboituneesta annoksesta lähellä syntymätöntä lasta. Tietokonetomografia-angiografia (TTA) ja digitaalinen subtraktioangiografia (DSA) tutkimusten annosmittaukset tehtiin potilasvastineessa käyttäen RPLD:a. Elinannoksista laskettiin efektiivinen annos aivovaltimoiden ja aivokaulavaltimoiden angiografiatutkimuksille. RPL -annosmittausmenetelmän havaittiin olevan lineaarinen ja annoksen häviäminen mittarista on vähäistä. Matalan annoksen mittausraja oli 20 µGy 12.2% toistettavuudella. RPLD on riippumaton säteilyenergiasta radiologiassa käytettävällä energia-alueella. Seitsemän potilaan keskimääräinen absorboitunut annos oli 11.2 mGy (vaihteluväli 2.2–28.7 mGy) emättimen pohjukasta mitattuna. Annostaso osoittaa, että katetrointitoimenpide on matala-annostutkimus, kun toimenpide tehdään läpivalaisuohjauksessa, eikä angiografisia kuvia käytetä. Aivovaltimoiden TTA:n efektiivinen annos oli viidesosa DSA menetelmän annoksesta. Aivokaulavaltimoiden TTA:n efektiivinen annos oli arviolta 35% korkeampi kuin DSA menetelmän annos. Konversiokertoimet DAP ja DLP yksiköistä efektiivisen annoksen laskemiseksi määritettiin tutkimuksessa käytetyille kuvausohjelmille. RPL -menetelmä osoitti riittävää luotettavuutta radiologisten säteilyannosten mittauksessa.

Avec l’avènement de l’ère intellectuelle et de l’Internet of Everything (IoE), les besoins de la communication mondiale et des applications diverses ont explosé. Cette révolution exige que les futurs réseaux de communication soient plus efficaces, intellectuels, agiles et évolutifs. De nombreuses technologies réseau sont apparues pour répondre à la tendance des réseaux de communication de nouvelle génération tels que les réseaux optiques élastiques (EONs) et la virtualisation de réseau. De nombreux défis apparaissent avec les apparences de la nouvelle architecture et de la nouvelle technologie, telles que le routage et l’allocation de ressource spectrale (RSA) dans les EONs et l’intégration de réseaux virtuels (Virtual Network Embedding ou VNE) dans la virtualisation de réseau.Cette thèse traite la conception et l’analyse d’algorithmes d’approximation dans trois problèmes d’optimation du RSA et du VNE : les impacts de la distribution du trafic et de la topologie du réseau sur le routage tout optique, de l’allocation de ressource spectrale, et du VNE dans les topologies des chemins et cycles. Pour le routage tout optique, le premier sous-problème du RSA, il y a toujours un problème en suspens concernant l’impact de la distribution du trafic et de la topologie EON. Comme le routage tout optique joue un rôle essentiel pour la performance globale de la RSA, cette thèse fournit une analyse approfondi théorique sur ces impacts. Pour le deuxième sous-problème du RSA, l’allocation de ressource spectrale, deux chemins optiques quelconques partageant des fibres optiques communes pourraient devoir être isolés dans le domaine spectral avec une bande de garde appropriée pour empêcher la diaphonie et / ou réduire les menaces de sécurité de la couche physique. Cette thèse considère le scénario dans lequel les exigences de bandes de garde réelles optiques sont différentes pour différentes paires de chemins, et étudie comment affecter les ressources spectrales efficacement dans une telle situation. L’hétérogénéité de la topologie des demandes de réseau virtuel (VNR) est un facteur important qui entrave les performances de la VNE. Cependant, dans de nombreuses applications spécialisées, les VNR ont des caractéristiques structurelles communes par exemple, des chemins et des cycles. Pour obtenir de meilleurs résultats, il est donc essentiel de concevoir des algorithmes dédiés pour ces applications en tenant compte des caractéristiques topologiques. Dans cette thèse, nous prouvons que les problèmes VNE dans les topologies de chemin et de cycle sont NP-difficiles. Afin de les résoudre, nous proposons des algorithmes efficaces également analysons leurs ratios d’approximation / With the coming of intellectual era and Internet of Everything (IoE), the needs of worldwide communication and diverse applications have been explosively growing. This information revolution requires the future communication networks to be more efficient, intellectual, agile and scalable. Many technologies have emerged to meet the requirements of next generation communication networks such as Elastic Optical Networks (EONs) and networking virtualization. However, there are many challenges coming along with them, such as Routing and Spectrum Assignment (RSA) in EONs and Virtual Network Embedding (VNE) in network virtualization. This dissertation addresses the algorithm design and analysis for these challenging problems: the impacts of traffic distribution and network topology on lightpath routing, the distance spectrum assignment and the VNE problem for paths and cycles.For lightpath routing, the first subproblem of the RSA, there is always a pending issue that how the changes of the traffic distribution and EON topology affect it. As the lightpath routing plays a critical role in the overall performance of the RSA, this dissertation provides a thoroughly theoretical analysis on the impacts of the aforementioned two key factors. To this end, we propose two theoretical chains, and derive the optimal routing scheme taking into account two key factors. We then treat the second subproblem of RSA, namely spectrum assignment. Any two lightpaths sharing common fiber links might have to be isolated in the spectrum domain with a proper guard-band to prevent crosstalk and/or reduce physical-layer security threats. We consider the scenario with diverse guard-band sizes, and investigate how to assign the spectrum resources efficiently in such a situation. We provide the upper and lower bounds for the optimal solution of the DSA, and further devise an efficient algorithm which can guarantee approximation ratios in some graph classes.The topology heterogeneity of Virtual Network Requests (VNRs) is one important factor hampering the performance of the VNE. However, in many specialized applications, the VNRs are of some common structural features e.g., paths and cycles. To achieve better outcomes, it is thus critical to design dedicated algorithms for these applications by accounting for topology characteristics. We prove the NP-Harness of path and cycle embeddings. To solve them, we propose some efficient algorithms and analyze their approximation ratios.

<p align="justify">Plusieurs métaux de notre vie courante sont obtenus industriellement au moyen de procédés électrolytiques. Un des procédés les plus communs est l’électro-obtention de cuivre, dans lequel le métal est déposé à la cathode tandis que l'oxygène se dégage à l'anode. Généralement, en usine, plusieurs anodes et cathodes, ayant une surface de 1 m2 et séparées par plus ou moins 10 cm sont alternées dans une cellule contenant une solution d'acide sulfurique riche en sulfate de cuivre. En fonction des conditions d'utilisation, les cathodes sont remplacées, après un certain temps, par des nouvelles de façon à récupérer le cuivre déposé. De ce fait, les anodes doivent être capables de résister sans se corroder, se déformer ou perdre leurs propriétés électrocatalytiques pendant de longues périodes. Au début, des alliages en Pb (pb-Ag, Pb-Ca-Sn,...) ont été utilisés comme anodes. Malheureusement, malgré leur faible prix, ces anodes présentent des surtensions élevées et une faible résistance à la corrosion et au fluage. Par conséquent, une alternative aux anodes traditionnelles en 1 développée. Ce nouveau type d'anode, connu sous le nom d’anode dimensionnellement stable (DSA) est fabriquée à partir d'une tôle en Ti recouverte par un mélange d'oxydes de métaux nobles catalysant la réaction de dégagement d'oxygène. Différentes techniques peuvent être utilisées pour préparer la couche d'oxyde. La technique la plus souvent employée consiste à décomposer thermiquement une solution de chlorures contenant un ou plusieurs nobles. Malheureusement, ce type d'anode est cher et a tendance à perdre son activité électrocatalytique avec le temps.</p> <p align="justify">Dans le but de produire une DSA à faible prix, pouvant résister de longues périodes sans se passiver, un nouveau type de DSA a été développé dans le présent travail. Cette anode est produite par électrodépôt d'un métal noble dans les pores d'un substrat microporeux en Ti/TiO2.</p> <p align="justify">Ce travail a permis de démontrer qu'une DSA avec une concentration en métal noble peut être obtenue par la voie proposée. Il a été montré que les propriétés électriques et électrochimiques de ces DSAs sont directement liées aux caractéristiques morphologiques et structurales du en Ti/TiO2. Lorsque la couche barrière existant au fond des pores est suffisamment fine et que le film présente des défauts, la résistance me l'interface Ti/métal noble est faible. Ceci abouti à des DSAs possédant d'excellentes propriétés électrocatalytiques. Les DSAs optimales sont capables de résister à des conditions similaires à celles employées en industrie avec des surtensions de ~ 0.4 V, ce qui représente un gain de 50% par rapport aux surtensions normalement atteintes par les anodes traditionnelles en Pb.</p>

Os disruptores endócrinos são frequentemente relatados na literatura como contaminantes de ambientes aquáticos. Por isso, os processos oxidativos avançados (POAs) têm sido estudados como alternativa para o tratamento em meio aquoso. Os POAs consistem na oxidação de compostos orgânicos por radicais hidroxilas com alto poder oxidante. Diante desses aspectos, o presente trabalho tem como principal objetivo o estudo da degradação do metil parabeno (MeP) por processos Fenton, utilizando planejamento experimental e a análise dos modelos matemáticos, possibilitando a avaliação da influência das variáveis e determinando as melhores condições. As degradações de 300 mL de 100 mg L-1 de MeP com o processo Fenton foram realizadas em um reator de vidro onde as concentrações ótimas foram: 16 mg L-1 de Fe2+, 62 mg L-1 de H2O2, pH = 3, agitação constante e 30°C chegando a 100% de degradação em 20 minutos. Para o foto-Fenton, as degradações foram de 500 mL de 100 mg L-1 de MeP em um reator com lâmpada de mercúrio de 4 W , utilizando-se uma concentração de 4 mg L-1 de Fe2+ e 52 mg L-1 de H2O2, pH = 3, 30°C e agitação constante chegando a 100% de degradação em 16 minutos. Finalmente a degradação de 300 mL de 100 mg L-1 de MeP por eletro- Fenton foi realizada em um reator, com 4 mg L-1 de Fe2+, com densidade de corrente (j = 25 mA cm-2) para a produção de H2O2 com eletrodos ADE(cátodo), platina(ânodo), 0,05 mol L-1 de Na2SO4 como eletrólito suporte, pH = 3, sob agitação constante e 30°C chegando a 100% de degradação em 11 minutos. A eficiência da degradação de MeP foi monitorada por espectroscopia UV-VIS e cromatografia liquida de alta eficiência (CLAE) e, a mineralização, pelo monitoramento do carbono orgânico total (COT). / Endocrine disruptors are frequently reported in the literature as contaminants of aquatic environments. Therefore, the advanced oxidation processes (AOPs) have been studied as an alternative to aqueous media treatments. AOPs involve the oxidation of organic compounds by hydroxyl radicals with high oxidation power. Considering these aspects, the aim of the present work is to study the methyl paraben (MeP) degradation by Fenton processes using experimental design and analysis of mathematical models, allowing the evaluation of the influence of variables and determining the best conditions. The degradation of 300 mL of 100 mg L-1 of MeP with Fenton process was performed in a glass reactor where the optimal concentrations were 16 mg L-1 of Fe2+, 62 mg L-1 of H2O2, pH = 3, constant stirring and T = 30°C, reaching 100 % degradation in 20 minutes . For the photo-Fenton degradations were 500 mL of 100 mg L-1 of MeP in a reactor with a mercury lamp with 4 W, using concentration of 4 mg L-1 of Fe2+, 52 mg L-1 of H2O2, pH = 3 , T = 30°C and constant stirring, reaching 100 % biodegradation in 16 minutes. Finally, the degradation of 300 mL of 100 mg L-1 of MeP by electro-Fenton was carried out in a reactor with 4 mg L-1 of Fe2+ with current density (j = 25 mA cm-2) for the production of H2O2 with ADE electrodes (cathode), platinum (anode), 0.05 mol L-1 Na2SO4 as supporting electrolyte, pH = 3, T = 30°C and constant stirring, to reaching 100 % degradation in 11 minutes. The degradation efficiency of MeP was monitored by UV- VIS spectroscopy and liquid chromatography (HPLC) and mineralization, by monitoring the total organic carbon (TOC).

A presen&ccedil;a de defensivos agr&iacute;colas no meio ambiente, mesmo que em baixas concentra&ccedil;&otilde;es (ng L-1/ &#956;g L-1), representa uma potencial fonte de perturba&ccedil;&atilde;o end&oacute;crina para os seres vivos. Neste cen&aacute;rio, destacam-se os herbicidas alaclor e atrazina, que s&atilde;o amplamente utilizados no combate a ervas daninhas. Entretanto, a Ag&ecirc;ncia de Prote&ccedil;&atilde;o Ambiental dos Estados Unidos (EPA) classifica como carcinog&ecirc;nicos, desreguladores end&oacute;crinos e seu limite, em &aacute;gua, n&atilde;o pode ultrapassar 2 e 3 &#956;g L-1, respectivamente. O objetivo deste trabalho foi estudar a degrada&ccedil;&atilde;o eletroqu&iacute;mica do alaclor e atrazina, utilizando uma c&eacute;lula do tipo filtro-prensa, e um &acirc;nodo dimensionalmente est&aacute;vel (ADE) de composi&ccedil;&atilde;o nominal Ti/Ru0,3Ti0,7O2, pH inicial fixo em 3 e a temperatura em 25 &ordm;C, uma vez que, os m&eacute;todos convencionais de tratamento n&atilde;o s&atilde;o totalmente eficientes na remo&ccedil;&atilde;o destes compostos org&acirc;nicos nos sistemas aquosos. Inicialmente realizou-se apenas a degrada&ccedil;&atilde;o eletroqu&iacute;mica do herbicida alaclor (100 mg L-1) via planejamento fatorial de ponto central do tipo 32, tendo como vari&aacute;veis, a concentra&ccedil;&atilde;o do eletr&oacute;lito suporte cloreto de s&oacute;dio (0,05, 01 e 0,15 g L-1) e a densidade de corrente (10, 30 e 50 mA cm-2), obtendo como melhor resposta, 93,45 % de remo&ccedil;&atilde;o e 71,6 % de mineraliza&ccedil;&atilde;o, ao usar CNaCl de 0,15 g L-1 e 50 mA cm-2. Por&eacute;m, a CNaCl de 0,15 g L-1 e densidade de 30 mA cm-2 foi escolhida como a melhor condi&ccedil;&atilde;o estudada, em virtude do seu menor valor de consumo energ&eacute;tico e por apresentar a taxa de remo&ccedil;&atilde;o (93,6%) e mineraliza&ccedil;&atilde;o (71,24%) pr&oacute;ximas ao uso da maior densidade de corrente. S&oacute; ent&atilde;o, na melhor condi&ccedil;&atilde;o, obtida previamente a partir dos experimentos de degrada&ccedil;&atilde;o do alaclor, que realizou-se a oxida&ccedil;&atilde;o de 100 mg L-1 de atrazina e da mistura dos herbicidas. Tamb&eacute;m foi observado uma cin&eacute;tica de pseudo primeira ordem na oxida&ccedil;&atilde;o dos herbicidas, e, al&eacute;m disso, foi realizada a identifica&ccedil;&atilde;o dos intermedi&aacute;rios e/ou produtos de degrada&ccedil;&atilde;o do alaclor e atrazina atrav&eacute;s da t&eacute;cnica de CLAE acoplada a um espectr&ocirc;metro de massas. / The pesticides presence in environment represents a potential endocrine disturbance source for the living beings, even in low concentrations (ng L-1/ &#956;g L-1). The herbicides alachlor and atrazine are important to highlight, these herbicides are widely used to combat weeds herbs. However, the Environmental Protection Agency (EPA) classifies alachlor and atrazine as carcinogens, endocrine disruptors and their water limit may not exceed 2 and 3 &#956;g L-1, respectively. The aim of this work was to study the electrochemical degradation of alachlor and atrazine, using a filter-press cell, and a dimensionally stable anode (DSA) with a nominal composition Ti/Ru0.3Ti0.7O2, fixed initial pH of 3 and temperature of 25&ordm;C. The conventional treatment methods are not completely effective to remove these organic compounds in aqueous systems. Initially, only an electrochemical degradation of alachlor (100 mg L-1) was made by factorial design center point type 32, considering as variables: the supporting electrolyte sodium chloride concentration (0.05, 0.1 and 0.15 g L-1) and current density (10, 30 and 50 mA cm-2). In this initial degradation was obtained as better result: 93.45% of removal and 71.6% of mineralization of alachlor, using CNaCl of 0.15 g L-1 and 50 mA cm-2. However, CNaCl of 0.15 g L-1 and a density of 30 mA cm-2 was chosen as the best condition studied, in the reason of its lower energy consumption value and presents a removal rate (93.6%) and the mineralization (71.24%) closer to the use of higher current density. The electrolyses of 100 mg L-1 of atrazine and the herbicides mixture were performed only in the best condition, previously obtained with alachlor degradation experiments. In addition, a kinetic of pseudo first order for both herbicides and their mixture oxidation was observed, and besides, the identification of intermediates and/or degradation products of alachlor and atrazine was performed by liquid chromatography coupled to mass spectrometry (LC-MS).

Este trabalho investigou a oxidação eletroquímica do ácido tânico em eletrodos do tipo Ânodo Dimensionalmente Estáveis (ADE) a base de SnO2 e IrO2 e eletrodos de Diamante Dopado com Boro (BDD). As eletrólises foram feitas em modo galvanostático em função de parâmetros como densidade de corrente e concentração de cloreto. A oxidação eletroquímica do ácido tânico foi capaz de promover a diminuição da concentração de fenóis totais, Carbono Orgânico Total (COT) e Demanda Química de oxigênio (DQO). Para os ADE os melhores resultados de remoção de Carbono Orgânico Total (COT) foram nas condições em que se utilizou 300 mg L-1 de cloreto e densidade de corrente de 25 mA cm-2. No entanto houve a formação de compostos organoclorados que não foram degradados com maiores tempo de reação. Para os eletrodos de BDD, obteve-se a remoção de aproximadamente 98% de COT após 10 horas de reação à 75 mA cm-2, na ausência de cloreto. Maiores remoções de COT são obtidas com o aumento da densidade de corrente. Eletrólises na presença de cloreto removeram quase 100% do COT em tempos menores de reação. Análises de compostos organohalogenados (AOX) mostraram que não houve a formação de compostos organoclorados. Menores densidades de corrente apresentaram maiores Eficiência de Corrente (EC) e menor Consumo de Energia (CE). As eletrólises na presença de cloro apresentaram melhores resultados de EC que na ausência do mesmo. A oxidação fotoeletroquímia do ácido tânico em eletrodos do tipo ADE de composição nominal Ti/ Sn0,7 Ir0,3 O2 também foi investigada nesse trabalho. O tratamento fotoeletroquímico foi realizado utilizando uma lâmpada de vapor de mercúrio de alta pressão de 125 W como fonte de irradiação. A variação da corrente não mostrou diferença significativa na oxidação do ácido tânico. A variação da concentração de cloreto no eletrólito suporte influenciou de forma acentuada a oxidação do ácido tânico. O tratamento fotoeletroquímico se mostrou mais eficiente na remoção de COT que os tratamentos eletroquímico e fotoquímico. No tratamento fotoeletroquímico ocorreu a formação de AOX no início da reação, no entanto com o passar do tempo esses compostos foram degradados. / This study investigated the electrochemical oxidation of tannic acid on electrodes of the Dimensionally Stable Anode (DSA) type based on SnO2 and IrO2 as well as on boron doped diamond (BDD) electrodes. The electrolyses were performed in the galvanostatic mode, as a function of such parameters as current density and chloride concentration. The electrochemical oxidation of tannic acid was able to promote the reduction of the concentration of total phenolics, total organic carbon (TOC), and chemical oxygen demand (COD). For the DSA the best results of Total Organic Carbon (TOC) removal were achieved at 300 ppm chloride and current density of 25 mA cm-2. However, organochlorine compounds were formed and were not degraded with increased reaction times. For the BDD electrodes, the removal of approximately 98% TOC was obtained after 10 hours of reaction at 75 mA cm-2, in the absence of chloride. Major TOC removals were obtained with increasing current density. Electrolyses in the presence of chloride removed almost 100% TOC in shorter reaction times. Analysis of organohalogen compounds (AOX) showed no formation of organochlorine compounds. Lower current densities led to higher current efficiency (CE) and lower Energy Consumption (EC). The electrolyses in the presence of chlorine produced better CE results than those performed in the absence of chlorine. The photoelectrochemical oxidation of tannic acid in ADE-type electrodes of nominal composition Ti / Sn0.9 Ir0.3 O2 was also investigated in this work. The photoelectrochemical treatment was performed using a high pressure mercury vapor lamp 125 W as the source of irradiation. The variation in current revealed no significant difference in the oxidation of tannic acid. The variation in chloride concentration in the electrolyte markedly influenced the oxidation of tannic acid. The photoelectrochemical treatment was more efficient for TOC removal than the electrochemical and photochemical treatments. Formation of AOX occurred at the beginning of the photoelectrochemical treatment, but over time these compounds were degraded.

Os disruptores endócrinos são frequentemente relatados na literatura como contaminantes de ambientes aquáticos. Por isso, os processos oxidativos avançados (POAs) têm sido estudados como alternativa para o tratamento em meio aquoso. Os POAs consistem na oxidação de compostos orgânicos por radicais hidroxilas com alto poder oxidante. Diante desses aspectos, o presente trabalho tem como principal objetivo o estudo da degradação do metil parabeno (MeP) por processos Fenton, utilizando planejamento experimental e a análise dos modelos matemáticos, possibilitando a avaliação da influência das variáveis e determinando as melhores condições. As degradações de 300 mL de 100 mg L-1 de MeP com o processo Fenton foram realizadas em um reator de vidro onde as concentrações ótimas foram: 16 mg L-1 de Fe2+, 62 mg L-1 de H2O2, pH = 3, agitação constante e 30°C chegando a 100% de degradação em 20 minutos. Para o foto-Fenton, as degradações foram de 500 mL de 100 mg L-1 de MeP em um reator com lâmpada de mercúrio de 4 W , utilizando-se uma concentração de 4 mg L-1 de Fe2+ e 52 mg L-1 de H2O2, pH = 3, 30°C e agitação constante chegando a 100% de degradação em 16 minutos. Finalmente a degradação de 300 mL de 100 mg L-1 de MeP por eletro- Fenton foi realizada em um reator, com 4 mg L-1 de Fe2+, com densidade de corrente (j = 25 mA cm-2) para a produção de H2O2 com eletrodos ADE(cátodo), platina(ânodo), 0,05 mol L-1 de Na2SO4 como eletrólito suporte, pH = 3, sob agitação constante e 30°C chegando a 100% de degradação em 11 minutos. A eficiência da degradação de MeP foi monitorada por espectroscopia UV-VIS e cromatografia liquida de alta eficiência (CLAE) e, a mineralização, pelo monitoramento do carbono orgânico total (COT). / Endocrine disruptors are frequently reported in the literature as contaminants of aquatic environments. Therefore, the advanced oxidation processes (AOPs) have been studied as an alternative to aqueous media treatments. AOPs involve the oxidation of organic compounds by hydroxyl radicals with high oxidation power. Considering these aspects, the aim of the present work is to study the methyl paraben (MeP) degradation by Fenton processes using experimental design and analysis of mathematical models, allowing the evaluation of the influence of variables and determining the best conditions. The degradation of 300 mL of 100 mg L-1 of MeP with Fenton process was performed in a glass reactor where the optimal concentrations were 16 mg L-1 of Fe2+, 62 mg L-1 of H2O2, pH = 3, constant stirring and T = 30°C, reaching 100 % degradation in 20 minutes . For the photo-Fenton degradations were 500 mL of 100 mg L-1 of MeP in a reactor with a mercury lamp with 4 W, using concentration of 4 mg L-1 of Fe2+, 52 mg L-1 of H2O2, pH = 3 , T = 30°C and constant stirring, reaching 100 % biodegradation in 16 minutes. Finally, the degradation of 300 mL of 100 mg L-1 of MeP by electro-Fenton was carried out in a reactor with 4 mg L-1 of Fe2+ with current density (j = 25 mA cm-2) for the production of H2O2 with ADE electrodes (cathode), platinum (anode), 0.05 mol L-1 Na2SO4 as supporting electrolyte, pH = 3, T = 30°C and constant stirring, to reaching 100 % degradation in 11 minutes. The degradation efficiency of MeP was monitored by UV- VIS spectroscopy and liquid chromatography (HPLC) and mineralization, by monitoring the total organic carbon (TOC).

A presen&ccedil;a de defensivos agr&iacute;colas no meio ambiente, mesmo que em baixas concentra&ccedil;&otilde;es (ng L-1/ &#956;g L-1), representa uma potencial fonte de perturba&ccedil;&atilde;o end&oacute;crina para os seres vivos. Neste cen&aacute;rio, destacam-se os herbicidas alaclor e atrazina, que s&atilde;o amplamente utilizados no combate a ervas daninhas. Entretanto, a Ag&ecirc;ncia de Prote&ccedil;&atilde;o Ambiental dos Estados Unidos (EPA) classifica como carcinog&ecirc;nicos, desreguladores end&oacute;crinos e seu limite, em &aacute;gua, n&atilde;o pode ultrapassar 2 e 3 &#956;g L-1, respectivamente. O objetivo deste trabalho foi estudar a degrada&ccedil;&atilde;o eletroqu&iacute;mica do alaclor e atrazina, utilizando uma c&eacute;lula do tipo filtro-prensa, e um &acirc;nodo dimensionalmente est&aacute;vel (ADE) de composi&ccedil;&atilde;o nominal Ti/Ru0,3Ti0,7O2, pH inicial fixo em 3 e a temperatura em 25 &ordm;C, uma vez que, os m&eacute;todos convencionais de tratamento n&atilde;o s&atilde;o totalmente eficientes na remo&ccedil;&atilde;o destes compostos org&acirc;nicos nos sistemas aquosos. Inicialmente realizou-se apenas a degrada&ccedil;&atilde;o eletroqu&iacute;mica do herbicida alaclor (100 mg L-1) via planejamento fatorial de ponto central do tipo 32, tendo como vari&aacute;veis, a concentra&ccedil;&atilde;o do eletr&oacute;lito suporte cloreto de s&oacute;dio (0,05, 01 e 0,15 g L-1) e a densidade de corrente (10, 30 e 50 mA cm-2), obtendo como melhor resposta, 93,45 % de remo&ccedil;&atilde;o e 71,6 % de mineraliza&ccedil;&atilde;o, ao usar CNaCl de 0,15 g L-1 e 50 mA cm-2. Por&eacute;m, a CNaCl de 0,15 g L-1 e densidade de 30 mA cm-2 foi escolhida como a melhor condi&ccedil;&atilde;o estudada, em virtude do seu menor valor de consumo energ&eacute;tico e por apresentar a taxa de remo&ccedil;&atilde;o (93,6%) e mineraliza&ccedil;&atilde;o (71,24%) pr&oacute;ximas ao uso da maior densidade de corrente. S&oacute; ent&atilde;o, na melhor condi&ccedil;&atilde;o, obtida previamente a partir dos experimentos de degrada&ccedil;&atilde;o do alaclor, que realizou-se a oxida&ccedil;&atilde;o de 100 mg L-1 de atrazina e da mistura dos herbicidas. Tamb&eacute;m foi observado uma cin&eacute;tica de pseudo primeira ordem na oxida&ccedil;&atilde;o dos herbicidas, e, al&eacute;m disso, foi realizada a identifica&ccedil;&atilde;o dos intermedi&aacute;rios e/ou produtos de degrada&ccedil;&atilde;o do alaclor e atrazina atrav&eacute;s da t&eacute;cnica de CLAE acoplada a um espectr&ocirc;metro de massas. / The pesticides presence in environment represents a potential endocrine disturbance source for the living beings, even in low concentrations (ng L-1/ &#956;g L-1). The herbicides alachlor and atrazine are important to highlight, these herbicides are widely used to combat weeds herbs. However, the Environmental Protection Agency (EPA) classifies alachlor and atrazine as carcinogens, endocrine disruptors and their water limit may not exceed 2 and 3 &#956;g L-1, respectively. The aim of this work was to study the electrochemical degradation of alachlor and atrazine, using a filter-press cell, and a dimensionally stable anode (DSA) with a nominal composition Ti/Ru0.3Ti0.7O2, fixed initial pH of 3 and temperature of 25&ordm;C. The conventional treatment methods are not completely effective to remove these organic compounds in aqueous systems. Initially, only an electrochemical degradation of alachlor (100 mg L-1) was made by factorial design center point type 32, considering as variables: the supporting electrolyte sodium chloride concentration (0.05, 0.1 and 0.15 g L-1) and current density (10, 30 and 50 mA cm-2). In this initial degradation was obtained as better result: 93.45% of removal and 71.6% of mineralization of alachlor, using CNaCl of 0.15 g L-1 and 50 mA cm-2. However, CNaCl of 0.15 g L-1 and a density of 30 mA cm-2 was chosen as the best condition studied, in the reason of its lower energy consumption value and presents a removal rate (93.6%) and the mineralization (71.24%) closer to the use of higher current density. The electrolyses of 100 mg L-1 of atrazine and the herbicides mixture were performed only in the best condition, previously obtained with alachlor degradation experiments. In addition, a kinetic of pseudo first order for both herbicides and their mixture oxidation was observed, and besides, the identification of intermediates and/or degradation products of alachlor and atrazine was performed by liquid chromatography coupled to mass spectrometry (LC-MS).