La lithographie électronique multifaisceaux (ou multi e-beam) en cours de développement est pressentie comme une alternative à la photolithographie 193 nm à immersion (193i nm) pour la production des circuits intégrés des noeuds technologiques avancés (14 nm et au-delà). Elle se présente également comme un concurrent potentiel à la photolithographie sous rayonnement EUV (13,5 nm) qui, elle aussi, est en cours de développement. Cependant, le développement de cette technologie doit faire face à plusieurs obstacles. Parmi eux, on a la contamination des optiques électroniques induite par le redépôt des molécules dégazées de la résine au cours de l‟exposition. Ces dépôts conduisent à la croissance d‟une couche carbonée en surface et à l‟intérieur des trous de ces optiques. Cette couche de contamination a tendance à diminuer la transmission des optiques et, par conséquent, diminuer les performances lithographiques de l‟outil (débit, uniformité des CD, rugosité, etc.). Il est donc indispensable de comprendre les mécanismes qui gouvernent le dégazage et la croissance de la couche de contamination afin d‟être en mesure de prédire son rôle sur les dérives des procédés et de l‟équipement. Tel a été l‟axe conducteur de ces travaux de thèse. Dans un premier temps, nous avons réalisé l‟état de l‟art des travaux déjà effectués dans le cas de la technique de lithographie EUV. Ensuite, nous avons conçu et fabriqué un banc de tests et développé, en parallèle, les méthodologies permettant de réaliser les études de dégazage des résines et de contamination induite sur des dispositifs simulateurs d‟optiques électroniques, appelés « mimics ». Puis, dans les conditions opératoires similaires à la plateforme Matrix développée par MAPPER Lithography, nous avons évalué le dégazage des résines de différentes formulations et mesuré la contamination induite par chacune de ces formulations sur les mimics à l‟aide du banc de tests développé. Enfin, nous avons proposé un modèle analytique permettant de prédire la croissance du film de contamination à l‟intérieur des trous du mimic en fonction des paramètres d‟exposition. / The development of multiple e-beam lithography equipment is foreseen as an alternative to the 193i nm immersion photolithography for the advanced technological node (less than 14 nm). This next generation lithography is a potential challenger to the EUV (13.5 nm) lithography which is also under development. However, this technology faces important challenges in controlling the contamination of the electron optics due to the adsorption of molecules outgassed from resist under exposure and the subsequent formation of a carbonaceous film on optics surface. This contamination layer can lead to the transmission loss of the optics and, consequently, degrade the tool lithographic performances (throughput, CD uniformity, Line Width Roughness, etc.). It is thus important to understand the resist outgassing and induced contamination mechanisms in order to predict their effect on the process drifts. That was the driver axis of these thesis works. Firstly, we performed the state of the art related to the works already published in the EUV lithography case. Secondly, we designed and built-up an experimental setup and developed, in parallel, the methods allowing to study the mechanisms of resist outgassing and induced contamination on electron optics simulators, called “mimic”. Thirdly, we assessed the outgassing of several resist formulations in the same operating conditions as in the Matrix platform developed by MAPPER Lithography. We also measured the induced contamination layer on the mimics for each resist formulation using the developed experimental setup. And finally, we proposed an analytical model that allows to predict the contamination film growth inside mimic holes during exposure.

A contaminação de resíduos industriais é um grande problema ambiental relacionado ao desenvolvimento industrial e urbano atual. A região do Vale dos Sinos, RS tem um histórico preocupante no gerenciamento e na destinação final de resíduos industriais ali gerados. Este estudo foi realizado na Central de resíduos da UTRESA, no município de Estância Velha, e teve como objetivo o diagnóstico ambiental e a caracterização do comportamento geoquímico de contaminantes em solo e águas subterrâneas. A metodologia do estudo consistiu no mapeamento e caracterização geológica e hidrogeológica, instalação de poços de monitoramento e sondagens, amostragens de chorume, solo e águas subterrâneas e superficiais, análises físico-químicas de chorume, água e solo, ensaios de lixiviação e difratometria de raios-X em solo, ensaios de slug, diagnóstico ambiental, avaliação de risco e proposta de remediação da área de estudo. Foram instalados 25 poços de monitoramento, coletadas e analisadas 73 amostras (chorume, solo e águas). Os resultados obtidos mostram ampla contaminação do solo e da água subterrânea na área de influência do aterro de resíduos industriais da UTRESA, com intensidade variada nos diferentes contaminantes. Cromo, cloreto e nitrogênio amoniacal apresentam os níveis mais elevados de contaminação, o que reflete o maior conteúdo registrado nas amostras de chorume analisadas. Hidrocarbonetos de petróleo, cianetos e mercúrio exibem contaminações de baixa intensidade com ampla distribuição. Chumbo, cobre e bário, por outro lado, registram contaminação fraca e restrita a poucos locais. A contaminação do solo é registrada principalmente na zona subsaturada do aquífero, nos locais de convergência das águas pluviais situadas a nordeste e sul das células de deposição de resíduos, o que reflete a disseminação preferencial dos contaminantes pelo fluxo superficial seguido de infiltração no solo. Este processo de transporte de contaminação implica, também, em alto risco de contaminação das águas superficiais dos corpos receptores adjacentes. Os resultados dos ensaios de lixiviação indicam fraco potencial de contaminação das águas subterrâneas. A degradação ambiental registrada no local decorre das condições inadequadas de disposição e confinamento dos resíduos em células construídas a margem das normas técnicas, não atendendo as especificações de impermeabilização de base e topo e no dimensionamento dos taludes. / Contamination of industrial wastes represent a great environmental problem related to industrial and urban development. Historically the Vale dos Sinos region has adopted inadequate procedures in the management and final disposal of its industrial waste. This study was realized in the UTRESA landfill area to do an environmental diagnostic and to characterize the geochemical behavior of contaminants in soils and groundwater.The study was performed by geological and hydrogeological mapping, installation of monitoring wells and borings, sampling of landfill leachate, soil, groundwater and surface water, physical-chemical analysis of landfill leachate, water and soil, leaching tests and X-ray diffraction on the soil, slug tests, environmental diagnostic, risk evaluation and proposed remediation for the studied area. Twenty five monitoring wells were installed and were collected and analyzed 73 samples (landfill leachate, soil and waters). The results show widespread contamination of soil and groundwater in the influence area of UTRESA industrial waste landfill, with varying intensity in different contaminants. Chromium, chloride and ammonium have higher levels of contamination, which reflects the highest content recorded in the manure samples analyzed. Petroleum hydrocarbons, cyanide and mercury contamination exhibit low intensity with a wide distribution. Lead, copper and barium, on the other hand, show low contamination restricted to a few locations. Soil contamination is recorded mainly in the vadose zone of the aquifer, at the convergence locals of stormwater situated to the northwest and south of the waste disposal cells, showing the preferential spread of contaminants by surface flow followed by soil infiltration. This transport process of contaminants also results in high risk of contamination of adjacent streams. The results of leaching tests indicate low potential for groundwater contamination by dessortion of metals from the soil. Environmental degradation registered on the site results from the inadequate conditions of disposal and confinement of waste in the cells constructed without complying the technical standards.

A contaminação de resíduos industriais é um grande problema ambiental relacionado ao desenvolvimento industrial e urbano atual. A região do Vale dos Sinos, RS tem um histórico preocupante no gerenciamento e na destinação final de resíduos industriais ali gerados. Este estudo foi realizado na Central de resíduos da UTRESA, no município de Estância Velha, e teve como objetivo o diagnóstico ambiental e a caracterização do comportamento geoquímico de contaminantes em solo e águas subterrâneas. A metodologia do estudo consistiu no mapeamento e caracterização geológica e hidrogeológica, instalação de poços de monitoramento e sondagens, amostragens de chorume, solo e águas subterrâneas e superficiais, análises físico-químicas de chorume, água e solo, ensaios de lixiviação e difratometria de raios-X em solo, ensaios de slug, diagnóstico ambiental, avaliação de risco e proposta de remediação da área de estudo. Foram instalados 25 poços de monitoramento, coletadas e analisadas 73 amostras (chorume, solo e águas). Os resultados obtidos mostram ampla contaminação do solo e da água subterrânea na área de influência do aterro de resíduos industriais da UTRESA, com intensidade variada nos diferentes contaminantes. Cromo, cloreto e nitrogênio amoniacal apresentam os níveis mais elevados de contaminação, o que reflete o maior conteúdo registrado nas amostras de chorume analisadas. Hidrocarbonetos de petróleo, cianetos e mercúrio exibem contaminações de baixa intensidade com ampla distribuição. Chumbo, cobre e bário, por outro lado, registram contaminação fraca e restrita a poucos locais. A contaminação do solo é registrada principalmente na zona subsaturada do aquífero, nos locais de convergência das águas pluviais situadas a nordeste e sul das células de deposição de resíduos, o que reflete a disseminação preferencial dos contaminantes pelo fluxo superficial seguido de infiltração no solo. Este processo de transporte de contaminação implica, também, em alto risco de contaminação das águas superficiais dos corpos receptores adjacentes. Os resultados dos ensaios de lixiviação indicam fraco potencial de contaminação das águas subterrâneas. A degradação ambiental registrada no local decorre das condições inadequadas de disposição e confinamento dos resíduos em células construídas a margem das normas técnicas, não atendendo as especificações de impermeabilização de base e topo e no dimensionamento dos taludes. / Contamination of industrial wastes represent a great environmental problem related to industrial and urban development. Historically the Vale dos Sinos region has adopted inadequate procedures in the management and final disposal of its industrial waste. This study was realized in the UTRESA landfill area to do an environmental diagnostic and to characterize the geochemical behavior of contaminants in soils and groundwater.The study was performed by geological and hydrogeological mapping, installation of monitoring wells and borings, sampling of landfill leachate, soil, groundwater and surface water, physical-chemical analysis of landfill leachate, water and soil, leaching tests and X-ray diffraction on the soil, slug tests, environmental diagnostic, risk evaluation and proposed remediation for the studied area. Twenty five monitoring wells were installed and were collected and analyzed 73 samples (landfill leachate, soil and waters). The results show widespread contamination of soil and groundwater in the influence area of UTRESA industrial waste landfill, with varying intensity in different contaminants. Chromium, chloride and ammonium have higher levels of contamination, which reflects the highest content recorded in the manure samples analyzed. Petroleum hydrocarbons, cyanide and mercury contamination exhibit low intensity with a wide distribution. Lead, copper and barium, on the other hand, show low contamination restricted to a few locations. Soil contamination is recorded mainly in the vadose zone of the aquifer, at the convergence locals of stormwater situated to the northwest and south of the waste disposal cells, showing the preferential spread of contaminants by surface flow followed by soil infiltration. This transport process of contaminants also results in high risk of contamination of adjacent streams. The results of leaching tests indicate low potential for groundwater contamination by dessortion of metals from the soil. Environmental degradation registered on the site results from the inadequate conditions of disposal and confinement of waste in the cells constructed without complying the technical standards.

Cette thèse se propose d’étudier la façon dont l’idée de mineur traverse l’œuvre de Pier Paolo Pasolini, que ce soit dans son sens linguistique et littéraire (rapport aux langues et aux auteurs dits « mineurs »), sociopolitique (présence des subalternes et des minorités), ou encore spirituel (« mineur » au sens franciscain). L’ensemble de la vaste production artistique et critique de l’auteur italien que nous prenons en considération semble en effet guidé par le désir de porter à la lumière et de valoriser ce qui d’ordinaire est dénigré, oublié et situé au bas des hiérarchies, quelles qu’elles soient : paysans frioulans, sous-prolétaires romains, peuples du Tiers Monde, langues et cultures périphériques, etc. Les notions de « minore » (« mineur ») et de « minoranza » (« minorité ») paraissent d’autant plus significatives et pertinentes qu’elles sont utilisées et problématisées par l’écrivain-cinéaste, de ses premiers essais littéraires à ses derniers articles et scénarios, à des moments clés de son parcours. Elles se révèlent en outre étroitement liées aux périodes de profondes transformations socio-culturelles que traverse l’Italie, dont elles se font le reflet antithétique. Alors que le prétendu « miracle économique » bat son plein au cœur des années 1960, la notion de mineur, centrée autour de l’idée d’infériorité et d’humilité, cède la place à la notion plus politique et polémique de minorité. Si cette dernière reprend certains traits de la précédente, elle se définit davantage comme altérité radicale et puissance de contestation des modèles dominants, tout en accentuant l’esthétique et la poétique de la contamination, selon lesquelles humilis et sublimis sont indissociables. / This PhD thesis intends to explore how the idea of minor is present throughout Pier Paolo Pasolini’s works, in its linguistic and literary sense (linked to languages and authors called « minors »), in its socio-political sense (presence of the subalterns and the minorities), or even in its spiritual sense (« minor » according to Franciscans). The extensive artistic and critical production of the Italian author who we consider, seems in fact to be guided by the will of highlighting and promoting what is usually depreciated, forgotten and situated at lower levels in every hierarchy : Friulian peasants, Roman sub-proletarians, people from the Third World, outlying languages and cultures, etc. The notions of minor and minorities are particularly significant and relevant, given that they are used and questionned by the writer and the director from his first literary essays to his last articles and scenarios, in key moments of his career. Furthermore, they appear closely associated to the period of deep socio-cultural changes that Italy is experiencing, hence the contradicting images they convey. While the so-called « economic miracle » is triumphal in the sixties, the notion of « minor », centered on the idea of inferiority and humility, is replaced by the more political and polemical notion of minority. If this last notion has some characteristics of the former one, it should also be defined as a radical alterity and contesting power of the dominant models, at the same time keeping the emphasis on the contamination esthetic and poetics, whereby humilis and sublimis are inseparable.

Dans l'industrie des semi-conducteurs, les plaques de silicium sont stockées dans des containers, appelés FOUPs (Front Opening Unified Pod) conçus à base de matériaux polymères (PC, PEEK, COP, PEI). De tels matériaux sont capables de sorber des contaminants moléculaires volatils et de les relarguer ultérieurement en présence de plaques, entraînant de la défectivité. Cette thèse a pour but d'apporter une meilleure connaissance et compréhension de la contamination et décontamination moléculaire des FOUPs au travers de quatre axes d'étude : - La détermination de la nature, des sources et des niveaux des contaminants moléculaires des FOUPs. Les acides HF et HCl, ont été détectés au ppbv – ppmv, et apparaissent comme les contaminants critiques. - L'étude des mécanismes de sorption et dégazage de HF et HCl gazeux dans les polymères. Ils ont été caractérisés par l'établissement, pour la première fois, des coefficients de solubilité (~10-1 m3(STP).m-3. Pa-1) et de diffusion (~ 10-15 m2/s) dans les conditions industrielles (22°C, 40% RH, 1 atm). - L'évaluation expérimentale de l'efficacité du nettoyage des FOUPs par différentes méthodes de décontamination (AUD, DMS, APR) à partir de FOUPs volontairement contaminés en HF. La mise sous vide à 70°C permet de décontaminer partiellement le FOUP du contaminant piégé dans le volume du polymère tandis que le nettoyage humide ou la mise sous vide à froid ne peuvent enlever que la contamination de proche surface du FOUP. - L'établissement d'un modèle de contamination des polymères du FOUP, basé sur les lois de Fick et de Henry et utilisant les coefficients de solubilité et diffusion établis. Ce modèle a été proposé et implémenté sur Comsol Multiphysics. Pour la première fois, le comportement dynamique du contaminant dans l'atmosphère et dans les matériaux du FOUP au cours de différents événements de contamination et de décontamination du FOUP a été déterminé par simulation numérique. Ainsi, les profondeurs de diffusion de la contamination dans les polymères ont été évaluées (de quelques dizaine à centaines de µm 48 h après un événement de contamination) ou encore l'efficacité de décontamination de méthodes de nettoyage a pu être estimée. / In the microelectronics industry, the silicon substrates (wafers) are stored in containers, named FOUP (Front Opening Unified Pod) made in polymers (PC, PEEK, COP, PEI). Such materials are able to sorb the volatile molecular contaminants and subsequently outgas these ones in presence of wafers, leading then to defectivity. This thesis aims to provide a better knowledge and comprehension of FOUP molecular contamination and cleaning, in focusing on four areas: - The determination of the nature, sources and levels of FOUP molecular contaminants. The HF and HCl acids, have been detected in ppbv – ppmv range, and appear as some critical contaminants. - The study of the sorption and outgassing mechanisms of HF and HCl gaseous in polymers. They have been characterized by the establishment, for the first time, of the solubility (~10-1 m3(STP).m-3. Pa-1) and diffusion coefficients (~ 10-15 m2/s) in industrial conditions (22°C, 40% RH, 1 atm). - The cleaning efficiency of different FOUP decontamination methods (AUD, APR, DMS) has been experimentally evaluated from intentionally contaminated FOUPs with HF. The vacuum at 70°C enables to partially decontaminate the contaminants trapped in polymer volume whereas the wet cleaning or the vacuum at ambient temperature can remove only contaminants on the near-surface of the FOUP materials. - The implementation of a model of FOUP polymer contamination, based on Fick and Henry laws and using the established solubility and diffusion coefficients. This model has been proposed and implemented on Comsol Multiphysics. For the first time, the dynamic behaviour of contaminant in the atmosphere and in the FOUP's materials during different contamination and decontamination events has been determined by numerical simulation. Thus the diffusion depth of the contaminant in polymeric materials has been evaluated (few tens to hundreds of µm 48 h after one contamination event) and also the decontamination efficiency of cleaning methods has been able to be predicted.

Ce travail présente l’étude d'une méthode de recherche utilisable en milieu industriel dessources de contamination chimique des pompes à vide équipant les lithographes EUV. Cetravail porte sur la problématique d’une éventuelle contamination carbonée introduite par lesystème de pompage et, notamment, par la turbine et le stator.A partir d’une caractérisation détaillée par chromatographie et spectroscopie dephotoémission de la contamination résiduelle issue du procédé de production, une procédured’analyse par spectrométrie de masse en phase gazeuse (RGA) utilisable en milieu industriel aété mise en oeuvre. En particulier, la possibilité de varier la température de l’échantillonpendant la mesure permet de caractériser la contamination carbonée résiduelle en étudiant lesprocédés physico-chimiques qui en sont à l’origine.Après avoir démontré l’efficacité du nettoyage final à éliminer les résidus des huiles de coupet avoir identifié la contamination organique résiduelle comme résidu du seul procédé denettoyage industriel, une copie « in vitro » de ce nettoyage a été développée : cela a permis demieux le caractériser en étudiant l’impact de plusieurs paramètres.L’influence de la concentration de lessive et de la procédure de séchage sur la contaminationcarbonée résiduelle a ainsi été étudiée. Une analyse de la contamination en phase gazeuse(RGA et TD-GCMS) ainsi qu’une caractérisation XPS de la surface des échantillons ont étéfaites. L’analyse de l’ensemble de ces résultats a permis d’établir un lien direct entre laconcentration de lessive utilisée et la contamination organique résiduelle. De plus,l’importance d’un séchage à haute température a été démontrée en mettant en évidence laprésence de plusieurs facteurs qui contribuent à la contamination résiduelle. / This work presents the study of a research method of the contamination sources of EUVLturbo molecular pumps, suitable for the industrial environment. This study deals with theproblem of a possible carbon contamination due to the pumping system and in particular tothe rotor and the stator.After a detailed characterisation of the production process residual contamination by TDGCMS/FID and XPS, a RGA procedure suitable for industrial environment has beendeveloped. The possibility to change the sample temperature during the measure lets tocharacterise the residual carbon contamination by investigating its primal physic-chemicalphenomena.The identification of the whole production process residual contamination demonstrates theefficacy of the industrial cleaning step to clean lubricants residuals. In order to bettercharacterise the cleaning step residual contamination, we developed an “in vitro” copy of theindustrial cleaning step.Thanks to the temperature variable RGA analysis of the residual contamination, we couldpoint out several contributions to carbon contamination and we could connect thesecontributions to different cleaning parameters.Detergent concentration as well as different drying procedure impact on residual carboncontamination has been studied. RGA and TD-GCMS/FID analysis as well as XPS surfacecharacterization have been performed. These analyses show a direct connection between thedetergent concentration used in the cleaning step and the residual carbon contamination.Furthermore, the importance of a high temperature drying step has been demonstrated.

Orientador: Adalberto Farache Filho / Banca: Maria da Penha Longo Mortatti Catanozi / Banca: Wellington Cyro de Almeida Leite / Resumo: Com a dúvida sobre a qualidade da água de abastecimento público, o cidadão passou a utilizar a água mineral com maior intensidade. Para atender a esta demanda as indústrias aumentaram a produção, novas empresas surgiram e também os falsários. Assim, é necessário conhecer-se a qualidade esperada e paga pelo consumidor nesse produto, realmente existe. O objetivo desta pesquisa foi avaliar aspectos de qualidade microbiológica em amostras de água mineral natural, não carbonatada, em garrafas individuais de 330mL a 600mL, das diversas marcas comercializadas em supermercados na cidade de Araraquara-SP. Foram utilizadas sessenta e nove amostras provenientes de dezessete marcas. As amostras foram adquiridas aleatoriamente, em épocas e estabelecimentos diferentes para que fossem originadas de lotes diversos. Para análise de coliformes totais e coliformes fecais/E. coli utilizou-se a técnica de substratos cromogênicos; para enterococos e Pseudomonas aeruginosa foram utilizadas as técnicas de tubos múltiplos específicas; para contagem de bactérias heterotróficas, foi utilizada a técnica de cultivo em profundidade. Todas as amostras de todas as marcas (100%) apresentaram ausência de coliformes fecais/E.coli, duas amostras (2,9%) de uma marca (5,9%) apresentaram contaminação por coliformes totais, duas amostras (2,9%), de duas marcas (11,8%) apresentaram contaminação por enterococos, três amostras (4,3%) de duas marcas (11,8%) apresentaram Pseudomonas aeruginosa e quarenta amostras (58%) de doze marcas (70,6%) apresentaram contagens acima de 500 UFC/mL para bactérias heterotróficas. Verificou-se que, das sessenta e nove amostras analisadas (100%) apenas seis (8,7%) apresentaram-se contaminadas com um ou mais dos indicadores especificados pela legislação brasileira para águas minerais. Entretanto, considerando os padrões para água mineral e o padrão...(Resumo completo, clicar acesso eletrônico abaixo) / Abstract: With the doubt on the water quality in public supplying, the citizen started to use the mineral water with larger intensity. For attend this demand the factory had increased the production, new companies had appeared and also the falsifiers. Thus, it's necessary to know if the quality waited and paid for the consumer in this product, really exists. The objective of the research was to evaluate aspects of microbiological quality in natural mineral water samples, not carbonated, in individual bottles of 330mL to 600mL, of the diverse marks commercialized in supermarkets in the city of Araraquara-SP. Sixty nine samples proceeding from seventeen marks had been used. The samples had been acquired aleatory, at different times and establishments for that they were originated from diverse lots. For analysis of fecal coliform/E. coli and total used it cromogenic substrate technique; for enterococcus and for Pseudomonas aeruginosa was used the technique of multiple tube specific; for counting of heterotrophic bacteria, was used the technique of culture in depth. All the samples of all the marks (100%) had presented absence for fecal coliform/E.coli., two samples (2.9%) of one mark (5.9%) had presented contamination for total coliform, two samples (2.9%), of two marks (11.8%) had presented contamination for enterococcus, three samples (4.3%) of two marks (11.8%) had presented Pseudomonas aeruginosa, and forty samples (58%) of twelve marks (70.6%) had presented counting above of 500 CFU/mL for heterotrophic bacteria. It was verified that, of the sixty nine analyzed samples (100%), only six (8.7%) had been presented contaminated with one or more than the pointers specified for the Brazilian legislation for mineral waters used in this research. However, considering the standards for mineral water and the standard for heterotrophic bacteria established by the legislation for water of human consumption...(Complete abstract click electronic access below) / Mestre

A contaminação de resíduos industriais é um grande problema ambiental relacionado ao desenvolvimento industrial e urbano atual. A região do Vale dos Sinos, RS tem um histórico preocupante no gerenciamento e na destinação final de resíduos industriais ali gerados. Este estudo foi realizado na Central de resíduos da UTRESA, no município de Estância Velha, e teve como objetivo o diagnóstico ambiental e a caracterização do comportamento geoquímico de contaminantes em solo e águas subterrâneas. A metodologia do estudo consistiu no mapeamento e caracterização geológica e hidrogeológica, instalação de poços de monitoramento e sondagens, amostragens de chorume, solo e águas subterrâneas e superficiais, análises físico-químicas de chorume, água e solo, ensaios de lixiviação e difratometria de raios-X em solo, ensaios de slug, diagnóstico ambiental, avaliação de risco e proposta de remediação da área de estudo. Foram instalados 25 poços de monitoramento, coletadas e analisadas 73 amostras (chorume, solo e águas). Os resultados obtidos mostram ampla contaminação do solo e da água subterrânea na área de influência do aterro de resíduos industriais da UTRESA, com intensidade variada nos diferentes contaminantes. Cromo, cloreto e nitrogênio amoniacal apresentam os níveis mais elevados de contaminação, o que reflete o maior conteúdo registrado nas amostras de chorume analisadas. Hidrocarbonetos de petróleo, cianetos e mercúrio exibem contaminações de baixa intensidade com ampla distribuição. Chumbo, cobre e bário, por outro lado, registram contaminação fraca e restrita a poucos locais. A contaminação do solo é registrada principalmente na zona subsaturada do aquífero, nos locais de convergência das águas pluviais situadas a nordeste e sul das células de deposição de resíduos, o que reflete a disseminação preferencial dos contaminantes pelo fluxo superficial seguido de infiltração no solo. Este processo de transporte de contaminação implica, também, em alto risco de contaminação das águas superficiais dos corpos receptores adjacentes. Os resultados dos ensaios de lixiviação indicam fraco potencial de contaminação das águas subterrâneas. A degradação ambiental registrada no local decorre das condições inadequadas de disposição e confinamento dos resíduos em células construídas a margem das normas técnicas, não atendendo as especificações de impermeabilização de base e topo e no dimensionamento dos taludes. / Contamination of industrial wastes represent a great environmental problem related to industrial and urban development. Historically the Vale dos Sinos region has adopted inadequate procedures in the management and final disposal of its industrial waste. This study was realized in the UTRESA landfill area to do an environmental diagnostic and to characterize the geochemical behavior of contaminants in soils and groundwater.The study was performed by geological and hydrogeological mapping, installation of monitoring wells and borings, sampling of landfill leachate, soil, groundwater and surface water, physical-chemical analysis of landfill leachate, water and soil, leaching tests and X-ray diffraction on the soil, slug tests, environmental diagnostic, risk evaluation and proposed remediation for the studied area. Twenty five monitoring wells were installed and were collected and analyzed 73 samples (landfill leachate, soil and waters). The results show widespread contamination of soil and groundwater in the influence area of UTRESA industrial waste landfill, with varying intensity in different contaminants. Chromium, chloride and ammonium have higher levels of contamination, which reflects the highest content recorded in the manure samples analyzed. Petroleum hydrocarbons, cyanide and mercury contamination exhibit low intensity with a wide distribution. Lead, copper and barium, on the other hand, show low contamination restricted to a few locations. Soil contamination is recorded mainly in the vadose zone of the aquifer, at the convergence locals of stormwater situated to the northwest and south of the waste disposal cells, showing the preferential spread of contaminants by surface flow followed by soil infiltration. This transport process of contaminants also results in high risk of contamination of adjacent streams. The results of leaching tests indicate low potential for groundwater contamination by dessortion of metals from the soil. Environmental degradation registered on the site results from the inadequate conditions of disposal and confinement of waste in the cells constructed without complying the technical standards.

Os metais de relevância toxicológica provenientes de fontes naturais e antropogênicas continuamente entram no ecossistema aquático causando sérios problemas à saúde humana e ambientais devido a sua toxicidade, longa persistência, bioacumulação e biomagnificação na cadeia alimentar. A contaminação de peixe e produtos da pesca por metais é de interesse da saúde pública. No Brasil, o Ministério da Saúde estabelece o limite máximo de tolerância (LMT) de 1,0 mg/kg para o arsênio em peixe e produtos da pesca e 0,5 mg/kg para o mercúrio, e 1,0 mg/kg em peixe predadores. O LMT não foi estabelecido para arsênio inorgânico, metilmercúrio e selênio. Este trabalho tem por objetivo avaliar a presença de arsênio total, arsênio inorgânico, mercúrio total, metilmercúrio e selênio em amostras de peixe cação comercializadas na cidade de São Paulo e analisar os resultados em relação à avaliação do risco. O arsênio total e o selênio foram determinados através de mineralização por via seca das amostras e quantificação utilizando absorção atômica com gerador de hidretos (FI-HG-AAS). O arsênio inorgânico foi determinado através de digestão ácida das amostras e posterior mineralização por via seca e quantificação utilizando FI-HG-AAS. O mercúrio total foi determinado através de digestão assistida por microondas em meio ácido e posterior quantificação do mercúrio total por espectrometria de fluorescência atômica com geração de vapor frio em fluxo contínuo (CV-AFS). O metilmercúrio foi determinado através de extração ácida das amostras e quantificação utilizando HPLC-termo-oxidação-CV-AFS. Os valores de As total nas amostras de cação analisadas variaram de 8,4 a 134,1 mg/kg (peso seco) e 2,1 a 33,5 mg/kg (peso úmido) e os valores de As inorgânico variaram de 0,013 a 0, 738 mg/kg (peso seco) e 0,0033 a 0,1845 mg/kg (peso úmido). Os valores de Hg total variaram de 0,7 a 14,6 mg/kg (peso seco) e 0,18 a 3,65 mg/kg (peso úmido). Os valores de metilmercúrio variaram de 0,46 a 8,67 mg/kg (peso seco) e 0,12 a 2,17 m/kg (peso úmido). Os valores de selênio variaram de 0,5 a 2,6 mg/kg (peso seco) e 0,13 a 0,65 mg/kg (peso úmido). Os valores de razão molar entre Hg e Se variaram de 0,28 a 5,39 (Hg:Se), e a média foi igual a 1,69. O PTWI para o arsênio inorgânico é 15 µg/kg de peso corpóreo (WHO, 1989), e assumindo uma média de peso corpóreo de 65kg, a ingestão de arsênio inorgânico proveniente do consumo de cação representa apenas 0,0007% do valor de referência TDI (Ingestão diária tolerável) para média brasileira. O PTWI para o Hg total é 5 µg/kg de peso corpóreo (WHO, 2003) e, a ingestão de Hg total por pessoa por dia proveniente apenas do consumo de cação para a média brasileira representa 0,17% do valor de referência TDI. / Metals of toxicological relevance from natural and anthropogenic sources continuously enter the aquatic ecosystem and cause serious environmental problems to human health and environment due to their toxicity, persistance, bioaccumulation and biomagnification in the food chain. Seafood metal contamination of is a public health interest. In Brasil, the Minister of Health establishes the maximum residue level (MRL) 1.0 mg/kg for arsenic in seafood and 0.5 for mercury and 1.0 for mercury in predator fish. The MRL was not stablished for inorganic arsenic, methylmercury and selenium. The purpose of this study is to evaluate the presence of total arsenic, inorganic arsenic, total mercury, methylmercury and selenium in shark samples commercialized in São Paulo city, and to evaluate their risk. The total arsenic and selenium were determined through sample dry ash and quantification by flow Injection -hydride generation-atomic absorption spectrometer (FI-HG-AAS). The inorganic arsenic was determined through sample acid digestion, ulterior dry ash and quantification by FI-HG-AAS. The total mercury was determined through sample acid digestion in microwave and quantification by atomic f1uorescence spectrophotometer with a cold vapor generator (CV-AFS). Methylmercury was determined by sample acid extraction and quantification by HPLC-termo-oxidation-CV-AFS. The levels of total arsenic vary between 8.4 and 134.1 mg/kg (dry weight) and 2.1 and 33.5 mg/kg (fresh weight) and levels of total inorganic arsenic vary between 0.013 and 0.738 mg/kg (dry weight) and 0.0033 and 0.1845 mg/kg (fresh weight). The levels of total mercury vary between 0.7 and 14.6 mg/kg (dry weight) and 0.18 and 3.65 mg/kg (fresh weight). The levels of methylmercury vary between 0.46 and 8.67 mg/kg (dry weight) and 0.12 and 2.17 m/kg (fresh weight). The levels of selenium vary between 0.5 and 2.6 mg/kg (dry weight) and 0.13 and 0.65 mg/kg (fresh weight). The values of molar reason between Hg and Se vary 0.28 and 5.39 (Hg:Se), and the media was 1.69. The PTWI for inorganic arsenic is 15 µg/kg body weight (WHO, 1989), and assuming an average body weight of 65 Kg, the ingestion of inorganic arsenic from shark ingestion represents only 0,0007% of the reference value TDI (Tolerable daily ingestion) for Brazilian media. The PTWI for total mercury is 5 µg/kg body weight (WHO, 2003) and the ingestion of total mercury per person per day from shark ingestion for Brazilian media represents 0.17% of the reference value TDI.

L'état des milieux aquatiques est un point essentiel de l'évaluation demandée par la Directive Cadre Européenne (DCE 2000/60/CE) visant à préserver ou à restaurer les masses d'eau superficielles et souterraines d'ici à 2015. A cet égard, les médicaments font désormais partis des contaminants organiques largement recherchés dans les eaux continentales de surface mais leur écodynamique sur tout un bassin versant est encore méconnue. Ce travail a ainsi apporté une évaluation de l'état de contamination de bassins versants par les médicaments à l'aide des biofilms épilithiques comme marqueur de l'imprégnation du milieu.La cartographie de l'imprégnation du bassin versant de la Vienne a permis de mettre en évidence une plus forte concentration en médicaments dans la partie amont du bassin que dans la partie aval (associée à la transition entre le socle granitique et les bassins sédimentaires). Les teneurs en médicaments mesurées dans les biofilms ont montré un facteur de concentration de 1000 par rapport aux teneurs rencontrées dans l'eau – traduisant ainsi un phénomène de bioaccumulation dans ce compartiment.L'hétérogénéité de l'habitat benthique (diversité des roches, différence d'exposition) influence le niveau d'imprégnation des biofilms sous certaines conditions d'exposition à un rejet.La majeure partie des biofilms situés en aval de l'ensemble des stations d'épuration est plus fortement contaminée. En revanche les mesures d'imprégnation effectuées sur le bassin de l'Arve n'ont montré aucun effet significatif de l'apport d'une station d'épuration recevant les effluents du Centre hospitalier Alpes Léman. / The European Water Framework Directive (DCE 2000/60/CE) aims to restore and protect aquatic ecosystems with the preservation of chemical and ecological status by 2015. In this sense, pharmaceuticals are part of organic contaminants currently investigated in surface waters but their fate along a watershed is still poorly known. This study has made an assessment of the contamination level of watersheds by pharmaceuticals using epilithic biofilms as a marker of the impregnation of the habitat.The impregnation mapping of the Vienne River watershed has highlighted a higher pharmaceutical concentration in the upper part of the river than in the lower part (associated with the transition from the granitic bedrock to the sedimentary basin). Pharmaceutical concentrations measured in the biofilms were 1000-fold higher than concentrations found in water – reflecting a phenomenon of bioaccumulation in this compartment.The habitat heterogeneity (rock diversity, exposure level) influences the impregnation degree of biofilms, depending on the exposure to point source pollution.Most biofilms located downstream from a wastewater treatment plant discharge were heavily contaminated with pharmaceuticals. On the other hand, the biofilms collected from the Arve River watershed have shown no significant effect of a wastewater treatment plant discharge receiving effluents from the hospital "Centre hospitalier Alpes Léman" on the impregnation of biofilms.