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Les PCB (polychlorobiphényles) sont des molécules connues pour leur longue demi-vie et leur forte liposolubilité qui conduisent à une bioaccumulation et une bioamplification dans les réseaux trophiques, menant à un potentiel risque pour les prédateurs de haut niveau tel que l’Homme. De plus, il a été démontré que leur affinité avec les composés lipidiques conduisaient à une transmission de la femelle à l’œuf chez les poissons. Dans ce contexte, et comme d’autres travaux ont déjà montré des effets des PCB sur la physiologie et le comportement d’animaux contaminés de différentes façons, nous avons observé les effets de ces molécules chez deux espèces, la sole commune et le poisson zèbre. La contamination a été réalisée via l’alimentation avec deux mélanges de PCB et deux concentrations qui correspondent à des situations environnementales, en termes de dose ou de choix et de proportion des congénères retenus. La dose la plus haute est équivalente à celle mesurée dans de la chair de molusques en baie de Seine et la dose intermédiaire à celle mesurée en estuaire de Loire. Les soles contaminées ont montré une diminution du niveau d’activité locomoteur après 30 jours (j) de contamination et une altération des capacités cryptiques après 60 j de contamination. Les poissons zèbre contaminés ont montré une augmentation de l’activité locomotrice après 250 j de contamination. La génération issue de cette génération de poisson zèbre contaminée a elle aussi montré une augmentation de l’activité locomotrice au stade larvaire et adulte. Chez les adultes, cela s’est traduit par une diminution de l’utilisation de la zone de fond des bacs et une augmentation du nombre de transition de zones, ce qui s’explique par une perte d’inhibition comportementale. Dans les deux cas, les phénotypes comportementaux observés chez les groupes PCB sont associés à une altération de la locomotion dans le sens d’une baisse d’activité pour une espèce placide comme la sole et dans le sens de l’augmentation pour une espèce mobile comme le poisson zèbre. / Because of their long biological half-life and high liposolubility, PCBs (polychlorinated biphenyls) are bioaccumulated and biomagnified through food chains over a wide range of trophic levels, leading to a potential risk for high trophic level predators including humans. Further, due to their binding with lipids, a demonstrated maternal transfer to eggs exists in fish. In this context, and since field analyses and experimental exposures have established links between PCBs exposure and alterations in physiology and behaviour of contaminated animals, we have examined the effects in both common sole and zebrafish species exposed through diets to two PCBs mixtures at two doses mimicking known environmental contamination levels and congener composition. The highest dose was equivalent to that found in molluscs flesh in the Seine Estuary and the intermediate dose was equivalent to that found in the Loire estuary. Contaminated soles showed a decreased locomotor activity level after 30 days (d) of contamination and altered cryptic abilities after 60 d of contamination. Contaminated zebrafish showed an increased locomotor activity level after 250 d of contamination. The offspring obtained from this contaminated generation of zebrafish showed an increase in swimming activity in larvae which was maintained in adults. In adults, this was associated with a decrease in tank bottom section occupancy and with an increase in the number of zone transition which may be due to a loosening of homebase behaviour and/or a loss of behavioural inhibition. In both cases, behavioural phenotypes observed in PCBs groups can be related to a disruption in locomotion activity towards decreased levels for a placid species like common sole and increased levels for a mobile species like zebrafish.

L’adsorption solide-liquide des PCB et des DDT constitue un moyen efficace pour leur récupération des eaux polluées à condition d’avoir une meilleure connaissance du mécanisme impliqué. Les cinétiques d’adsorption statique ont été principalement réalisées à 25 °C avec le2-PCB, un mélange de tétra-, penta- et hexa-CB et le 4,4’-DDT sur 3 charbons actifs (CA) en poudre différents par le précurseur (houille, bois) et le mode d’activation (H2O, H3PO4) dans l’eau, en présence ou non d’éthanol. Les résultats marquants ont été les suivants : L’adsorption du polluant sur le CA est d’autant plus favorisée que sa solubilité dans la phase liquide est plus faible. Ainsi, l’adsorption du polluant hydrophobe est très augmentée dans l’eau pure. L’adsorption des polluants favorisée par la microporosité développée est essentiellement un phénomène de surface où interviennent les forces de Van der Waals. Une bonne adéquation entre la taille des molécules et la largeur moyenne des pores en forme de fentes montre un confinement maximum des molécules dans la microporosité. L’interaction π−π entre adsorbat et adsorbant, favorisée par le nombre de Cl n’est pas à exclure. Enfin, nous avons montré par la cinétique dans les conditions initiales que l’adsorption y est limitée par le transfert de masse externe. Les modélisations par diffusion superficielle homogène (HSDM), conduisant aux coefficients de diffusion superficielle interne, ont montré que la cinétiqued’adsorption est presque complètement gouvernée par la diffusion intraparticulaire. / The solid-liquid adsorption of PCBs and DDT is an effective process for the recuperation of wastewaters but a better understanding of the involved mechanism is required. In this study, the static adsorption kinetics were mainly carried out at 25 ° C for 2-PCB, a mixture of tetra-, penta-and hexa-CB, and 4,4 '-DDT onto three different powdered activated carbons (AC) of the precursor (coal, wood) and the activation mode (H2O, H3PO4) in water, with or without ethanol. The prominent results were as follows: The adsorption of the pollutant on the AC is favored if its solubility in the liquid phase is lower. As a result, the adsorption of the hydrophobic pollutant is significantly increased in pure water. Moreover, the adsorption of pollutants favored by the developed microporosity is a surface phenomenon which involved the Van der Waals forces. A good fit between the size of molecules and the average width of the slit-shape pores gave a maximum confinement of molecules in the micropores. The π−π interaction between adsorbate and adsorbent, favored by the number of Cl, is not excluded. Finally, by studying the kinetics of the initial conditions, we found that the adsorption is limited by the external mass transfer. The internal surface diffusion coefficients estimated from applying the homogeneous surface diffusion models (HSDM) showed that the adsorption kinetics are almost completely governed by the intra-particle diffusion.

Este presente trabalho tem o objetivo de reconstruir a história do Movimento pela Emancipação do Proletariado (MEP), organização política que compôs o segundo momento da chamada Nova Esquerda, em meados dos anos 1970. Fazendo parte do tronco que tem em sua raiz a POLOP (Política Operária), o MEP compartilhava da visão que defendia o caráter socialista da revolução brasileira, uma vez que o Brasil possuía uma economia plenamente capitalista, embora atrasada e dependente dos centros metropolitanos da economia-mundo. Do ponto de vista teórico, o MEP seguia as formulações da Teoria da Dependência e as contribuições de autores como Caio Prado Júnior, Moniz Bandeira, Florestan Fernandes e Chico de Oliveira, dentre outros, para encontrar uma teoria da Revolução Brasileira. A partir dessas referências, a organização desenvolveu atuação clandestina contra a ditadura militar. Organizava-se com moldes no marxismo-leninismo e enxergava na classe operária o principal sujeito da revolução. Por fazer oposição ao regime, a organização foi vítima da máquina repressiva, sofrendo com prisões e tortura. O MEP desenvolveu atuação militante entre estudantes, professores, no meio operário e em bairros da periferia de grandes cidades e editou o jornal Companheiro. Além disso, atuou desde o início na fundação do Partido dos Trabalhadores. Em 1985, ao lado da Ala Vermelha do PCdoB e da Organização Comunista Democracia Proletária (OCDP), fundou o Movimento Comunista Revolucionário (MCR). / The present study aims to rebuild the story of Movimento pela Emancipação do Proletariado (Movement for the Emancipation of Proletariat - MEP), a political organization that integrated the second moment of the so called New Left, in the mid- 1970s. Stemming from POLOP (Política Operária), MEP shared a vision that advocated the socialist character of Brazilian Revolution, once the country had an enterely capitalist economy, albeit backward and depending on the metropolitan centers of the world economy. From a theoretical standpoint, MEP had followed the statements of Dependency Theory to develop a Brazilian Revolution theory based on the contributions of scholars like Caio Prado Júnior, Moniz Bandeira, Florestan Fernandes and Chico de Oliveira, among others. From these referencies, the organization have developed a clandestine practice against the Military Dictatorship. Grounded on Marxist-Leninist principles, MEP considered the working class as the revolution protagonist. As opponents of the regimen, the organization members were victims of the repressive apparatus, suffering persecution and torture. MEP developed a militant work between students, teachers, the labor movement and on the outskirts of big cities and edited the Companheiro newspaper. Furthermore, MEP participated in the Workers Party (PT) foundation. In 1985, along with PCdoB red wing and the Organização Comunista Democracia Proletária (OCDP), founded the Movimento Comunista Revolucionário (MCR).

Les polychlorobiphényles (PCB) et notamment les congénères les plus présents dans les sites et sols pollués, les PCB non dioxin like, constituent un danger sanitaire potentiel. Le risque associé est exacerbé chez le jeune enfant (6 mois à 3 ans) du fait, notamment, de son comportement exploratoire qui, de plus, a lieu durant une période critique de la croissance. L'objectif principal de cette thèse a été de caractériser l'impact des caractéristiques du sol sur la biodisponibilité relative des PCB. Les résultats in vivo ont montré l'impact des caractéristiques de la matière organique des sols sur la biodisponibilité relative des PCB par l'emploi de sols artificiels. Plusieurs matières organiques standardisées ont été testées allant des matières organiques solubles (acides fulviques, acides humiques) à une matière organique à la condensation maximale : le charbon actif. Ces éléments ont permis de montrer de larges variations de biodisponibilité relative allant d'une biodisponibilité relative nulle (charbon actif) à 100% (acide fulvique). Ces données soulignent l'importance de la condensation de la matière organique dans la rétention des PCB durant les processus digestifs. L'impact de caractéristiques (contenu en carbone organique, argile, black carbon, pH, concentrations en PCB) de sols historiquement contaminés sur la biodisponibilité a ensuite été évalué. Le taux de carbone organique et en black carbon sur la rétention des PCB. Toutefois la biodisponibilité relative demeure supérieure à 45% quel que soit le sol étudié. Les PCB sont donc peu retenus par le sol. Ainsi, l'exposition aux PCB via l'ingestion de sol semble proportionnelle à la quantité ingérée / Polychlorobiphenyls (PCBs) and, overall, non-dioxin-like PCBs (NDL-PCBs) the most abundant congeners in contaminated environmental matrices, constitute a potential health hazard. This risk is even more acute for young children (6 month to 3-year-old) because of their mouthing activities and because this exposure occurs during a critical part of their growth. The main objective of this thesis was to characterise the impact of soil's characteristics on the relative bioavailability of PCBs. The impact of the soil organic matter characteristics on the relative bioavailability of PCBs was assessed using artificial soils. Several standardised organic matters were tested ranging from soluble organic matters (fulvic acids, humic acids) to one organic matters highly condensed, activated carbon, a model of black carbon. These elements lead to show important variations in terms of relative bioavailability from 0% (activated carbon) to 100%, maximal relative bioavailability (fulvic acids). These findings highlight the importance of OM condensation in terms of PCB retention during the digestive processes. Then, the Impact of organic carbon, black carbon and clay content, pH, NDL-PCBs concentrations in historically contaminated soils on bioavailability and bioaccessibility was assessed. These approaches tended to show the importance of OC and BC content on retention of PCBs. Relative bioavailability was found to be higher than 45%, whatever the soil. Thus, PCBs retention in contaminated soils appears rather limited. Finally, exposure to PCBs via soil ingestion appears proportional to the quantity ingested

A reação de hidrodescloração catalítica (HDC) de bifenilas policloradas (PCB) foi estudada em diversos sistemas reacionais: solventes orgânicos, dióxido de carbono supercrítico, presença e natureza de aditivos (bases e co-solventes) a temperaturas na faixa de 25 °C a 100 °C e pressões de 1 bar até 250 bar. Os reagentes utilizados foram um composto modelo (2,4- diclorobifenil), misturas comerciais de PCB (Aroclor, Ascarel) e outros compostos halogenados (clorobenzenos e bromoclorobenzeno). Os catalisadores avaliados, paládio suportado em carvão ativo (Pd/C), paládio suportado em sílica mesoporosa (Pd/SiO2), nanopartículas ferromagnéticas de paládio (FFSiNH2Pd), e nanopartículas ocas de paládio (PdNP) e de platina (PtNP), mostraram-se versáteis nas mais diversas condições, quer sejam condições supercríticas, presença ou não de água, presença e natureza da base e diferentes doadores de hidrogênio. Em dióxido de carbono, dois regimes reacionais foram avaliados: dióxido de carbono subcrítico, onde o gás atua como agente expansor da fase líquida ao se dissolver nela permitindo que a reação ocorra em uma fase líquida rica em gás hidrogênio; e dióxido de carbono supercrítico, sistema onde a temperatura influencia fortemente a reação e a pressão tende a ter efeito negativo sobre a velocidade de reação, devido a efeitos de diluição e de competição das moléculas do gás com as moléculas dos reagentes. A condição reacional ótima foi determinada para o regime supercrítico e dados cinéticos foram obtidos para os regimes sub- e supercrítico. / The catalytic hydrodechlorination reaction (HDC) of polychlorinated biphenyls (PCB) was studied in several reactional systems: organic solvents, supercritical carbon dioxide, presence and nature of additives (bases and co-solvents), in temperatures of 25 °C to 100 °C and pressures of 1 bar to 250 bar. The reagents used were: a model compound, 2,4-dichlorobiphenyl, commercial mixtures of PCB (Aroclor, Ascarel) and other halogenated compounds (chlorobenzenes and bromochlorobenzene). The catalysts evaluated, palladium supported in activated carbon (Pd/C), palladium supported in mesoporous silica (Pd/SiO2), palladium ferromagnetic nanoparticles (FFSiNH2Pd), and hollow palladium ((PdNP) and platinum (PtNP) nanoparticles, showed to be versatile in several conditions, either supercritical conditions, presence or not of water, nature of the base, and different hydrogen donors. In carbon dioxide, two reaction regimes were evaluated: subcritical carbon dioxide, where the gas acts as an expansion agent of the liquid phase when it dissolves in it, allowing that the reaction happens in a liquid phase rich in hydrogen; and supercritical carbon dioxide, a system where the temperature has a strong influence over the reaction and the pressure has a negative effect on the rate of the reaction, due to dilution and the competition of gas molecules with the reagents molecules for the catalyst. The optimal reaction condition was determined for the supercritical regime and kinetic data were obtained for both the sub and supercritical regimes.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / No decorrer das últimas décadas a pesquisa relacionada à contaminação de organismos marinhos por compostos organoclorados (OCs) se intensificou aliada à utilização de algumas espécies como sentinelas da qualidade ambiental quanto aos poluentes orgânicos. Dentre essas espécies, podem-se destacar os cetáceos, animais que entre outras características possuem grande longevidade, alta porcentagem lipídica em seus tecidos e são predadores de topo de cadeia trófica, tendendo assim a acumular altos níveis de OCs em seus tecidos. O presente estudo teve por objetivo determinar as concentrações de OCs de origem industrial e agrícola (PCBs, HCB e DDTs) em tecido hepático de oito diferentes espécies de cetáceos delfinídeos pertencentes a três distintas áreas oceânicas do Estado do Rio de Janeiro, são elas a região costeira, a plataforma continental e a região oceânica. A determinação foi realizada em cromatógrafo a gás (GC - Agilent 6890) conectado a um espectrômetro de massa (MS - Agilent 5973). Os valores de DDTs (1263617272 ng.g -1 lip.) e PCBs (7648877288 ng.g -1 lip.) aqui encontrados estão entre os mais altos já reportados para o táxon. Em todas as áreas observou-se uma predominância do ΣPCB, seguida do ΣDDT e HCB, em níveis que refletem o caráter fortemente industrial da região analisada. Entre os PCBs, a maior contribuição advém dos hexabifenis, seguida dos hepta e pentabifenis, sendo os congêneres 153, 138 e 180 os principais em todas as áreas. A razão p,pDDE/ΣDp,pDDT foi alta em todas as regiões (0,9), refletindo um input antigo do poluente na área. Foram realizadas correlações entre as concentrações de OCs e os parâmetros biológicos das espécies, como idade, sexo e comprimento total. A transferência placentária de OCs foi analisada em dois pares de fêmea-feto de Sotalia guianensis, mostrando uma maior transferência dos compostos com menor log Kow. Como esperado, foi encontrada uma diferença significativa no perfil de contaminação entre as espécies das diferentes regiões, relacionada à proximidade da fonte, características espécie-específicas e ao arranjo trófico das espécies. / Over the past decades the research on marine organisms contamination by organochlorine compounds (OCs) has been intensified, allied to the utilization of some species as sentinels of the environmental quality related to organic pollutants. Among these species, cetaceans stand out as animals that, between other characteristics, have great longevity, high lipid percentage on their tissues and are top predators in food chains, therefore having the tendency to accumulate high OCs levels in their tissues. The present study aimed to determine OCs concentrations from industrial and agricultural sources (PCBs, HCB and DDTs) in hepatic tissue of eight different species of delphinid cetaceans belonging to three different oceanic areas of Rio de Janeiro State, namely, coastal region, continental shelf and oceanic region. The determination was performed in an Agilent 6890 gas chromatograph (GC) connected to an Agilent 5973 mass spectrometer (MS). DDTs (1263617272 ng.g -1 lip.) and PCBs (7648877288 ng.g -1 lip.) values reported here are amongst the highest values ever reported for the taxon. In all areas ΣPCB predominance was observed, followed by ΣDDT and HCB in levels that reflect the highly industrial character of the analyzed region. Amongst PCBs, the largest contribution comes from hexa biphenyls, followed by hepta and penta biphenyls, being the 153, 138 and 180 the main congeners in all areas. The p,pDDE/ΣDp,pDDT ratio was high in all regions (0,9), reflecting an ancient input of the pollutant in the area. Correlations between OCs concentrations and biologic parameters such as age, sex and total body lenght were performed. OCs placental transfer was analyzed in two Sotalia guianensis mother-fetus pairs, showing a higher transfer of compounds with lower log Kow. As expected, a significant difference was found on the contamination profile between species from the different regions, related to source proximity, species-specific characteristics and the species trophic arrangement.

Biochemical and biophysical methods in combination with electron microscopy were used to investigate structure and function of pigment-protein complexes in thylakoid membranes of various photosynthetic organisms.