The health of the Baltic Sea is negatively affected by hazardous substances such as metals and persistent organic pollutants (POPs), which include legacy pollutants that were banned decades ago, but still circulate in the ecosystem. Elevated levels of legacy pollutants, identified by HELCOM as key hazardous substances, have been found in accumulations of fibrous sediments, so-called fiberbanks and fiber-rich sediments, which derive from old pulp mills along the Swedish north coast. The fiberbanks are deposited in shallow water and bathymetrical models show evidence of their erosion, potentially caused by propeller wash, submarine landslides and gas ebullition. This thesis addresses the potential dispersal of key substances from three fiberbank sites located in a non-tidal Swedish estuary, in which metals and POPs are present in concentrations that may pose a risk for benthic organisms. Metals and POPs are partitioned to organic material and, as expected, show the highest partitioning coefficients (KD) in fiberbanks that have higher TOC levels compared to adjacent areas with fiber-rich sediments (natural clay sediments mixed up with fibers) or relatively unaffected postglacial clays. However, many analytes were found to be present in quantifiable concentrations in pore water, which indicates diffusion of substances from the solid phase to the aqueous phase. To assess the dispersive influence of an abrupt erosional event on dispersion, metals were measured in undisturbed bottom water and in bottom water disturbed by artificial re-suspension of fibrous sediments. The bioavailable, dissolved fraction of metals decreased in bottom water after re-suspension, probably due to the particle concentration effect. In contrast, the total concentrations of metals and number of quantifiable metals increased with particle concentration caused by re-suspension. At one station, the total concentration of chromium (Cr) was elevated to a level where it may lower the ecological status of the water body during periods of substantial erosion (e.g. spring floods or submarine landslides). Analyses of disturbed bottom water revealed, however, that minerogenic particles were preferentially re-suspended compared to organic. This suggests that physical erosion and re-suspension of fiberbank sediments might have a larger effect on dispersal of metals than on POPs. / TREASURE

La question des détritus marins de plastique et de leur impact sur l'environnement prend de l’ampleur. Il a été démontré que 80% des plastiques sont issus de sources terrestres, tandis que 20% viennent des côtes et mers. De nombreux auteurs soulignent un problème environnemental sérieux lié à l'absorption de POP (Polluants Organiques Persistants) par les débris plastiques, initiant ainsi une source potentielle de contamination de la chaîne alimentaire. Tous les auteurs attribuent la fragmentation en « microplastiques » (taille < 5mm) à des phénomènes liés à la dégradation, en particulier sous UV sans l’avoir jamais réellement ni démontré ni analysé. Les rivières constituant alors un vecteur privilégié de transport des déchets terrestres vers les mers et océans, nous avons décidé de mettre en évidence (et de quantifier) la présence de microplastiques dans une rivière réputée « sauvage » comme l’Allier. Au laboratoire, nous mettons au point des protocoles de simulation de la fragmentation des plastiques sous irradiations UV de différentes matières plastiques dans l'eau (douce). Nous analysons aussi bien les molécules chimiques issues de la dégradation des plastiques et transférées dans le milieu aqueux que les modifications moléculaires que peut subir le matériau. / The question of marine litter and their environmental impact gains importance. It was shown that 80% of plastics results from terrestrial sources, while 20% come from coastlines and seas. Many authors point to a serious environmental problem involved to the absorption of POPs (persistent organic pollutants) by plastic detritus, thus initiating a potential source of contamination of the food chain. All authors attribute the fragmentation to "microplastic" (size < 5mm) to phenomena related to degradation, under UV without ever having demonstrated or analysed it. The rivers constituting then a privileged vector of transport of the terrestrial waste towards the seas and oceans, we decided to highlight (and quantify) the presence of microplastics in a river known as "wild" as the Allier. At the laboratory, we develop simulation protocols for the fragmentation of plastics under UV irradiation of various plastic materials in fresh water. We analyse both the chemical molecules resulting from the degradation of plastics and transferred to the aqueous medium as well as the molecular changes that can undergo the material.

For 2010 the European Union has a goal to increase the share of renewable energyware to 12%. For 2020 the goal is 20%. One of visions to reach this is to raise the share of solid biofuels. Politicans all over ideologycal spectrum collectively propagate, that farming and waste management sector industry has developed ways to produce solid recovered fuels with reliable qualities, which are used successfully regarding economic and environmental aspects. One of prerequisites to reach this will be to achieve the standardization of solid biofuels. This leads to a need for flexible market, which is attainable only by common understanding concerning terminology, sampling and test methods. European energetically non-intensive industries and settlements are looking for ecologically friendly alternative fuels in order to save fossil fuels. And by doing so, enforce the development of fitting technical norms to facilitate the meeting of offer and demand for the product. Pressed biofuels like pellets are today playing the key role for the small house market as well as for large scale coal substitution in local power plants. The thesis is a part of scientific contemplation MSM 06/2/4a solved by professors S.Kužel and L.Kolář and is trying to answer the question: ``Is combustion of solid biofuels ecologically friendly?{\crqq}

Abstract Persistent organic pollutants (POPs), especially dioxin-like chemicals, have been shown to have adverse effects on skeleton and these effects are likely to be mediated via the aryl hydrocarbon receptor (AHR). In spite of the extensive research, the characteristics of developmental effects of POPs are poorly known and the role of AHR in POP bone toxicity and skeletal development in general. In this project changes in bone morphology and strength as well as tissue matrix mechanics are studied by applying state of the art biomedical engineering methods. This allows understanding of the effects of dioxins exposure and AHR activity on the development and maturation of extracellular matrix in musculoskeletal tissues from a completely new perspective, and thereby improving the health risk assessment of POPs. In the present study skeletal properties of rats exposed maternally to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), Northern Contaminant Mixture (NCM) and Aroclor1254 (A1254) were studied for cross-sectional morphometric and biomechanical properties, and data were analysed with benchmark dose modelling. In addition, extracellular matrix properties were analysed using nanoindentation. Similar measurements were performed for adult wild-type and AHR-null mice after TCDD exposure. The same animals were also analysed for microstructural changes using micro-computed tomography and their bone cell activity was estimated from serum markers and gene expression. Analyses show decreased bone length and cross-sectional properties with consequently decreased bone strength. On the other hand, an increased trabecular BMD in response to NCM and A1254 was observed. In addition, bone matrix properties indicated delayed maturation or early senescence after maternal or adult exposure, respectively. The AHR is mainly responsible for bone toxicity of dioxin-like compounds and plays a role in bone development. This is likely due to disturbed bone remodeling as indicated by altered serum markers and gene expression. Overall these results indicate that POPs decrease bone strength, but the interpretation is difficult as there is more trabecular bone within cortical bone with compromised quality and increased porosity. / Tiivistelmä Altistumisen pysyville orgaanisille ympäristökemikaaleille on todettu heikentävän luustoa. Dioksiinien ja dioksiininkaltaisten yhdisteiden vaikutusten on havaittu välittyvän aryylihiilivetyreseptorin (AHR) välityksellä. Huolimatta pitkään kestäneestä tutkimuksesta POP-yhdisteiden sikiönkehityksen aikaisen altistuksen vaikutukset ja etenkin niiden mekanismit ovat edelleen huonosti tunnettuja, samoin kuin AHR:n osuus POP-yhdisteiden luutoksisuudessa ja luuston kehityksessä ylipäätään. Tässä työssä tutkittiin luuston rakenteellisia ja mekaanisia ominaisuuksia niin perinteisillä kuin uusimmilla biolääketieteen tekniikan menetelmillä. Tutkimuksen tavoitteena on saada uutta tietoa POP-altistuksen ja AHR-aktiivisuuden vaikutuksista luuston kehitykseen ja luukudoksen ikääntymisprosesseihin, mikä edesauttaa kyseisten yhdisteiden riskinarviointia. Tutkimuksissa altistettiin kantavia rottaemoja 2,3,7,8-tetraklooridibenzo-p-dioksiinille (TCDD), pohjoiselle saasteseokselle ja kaupalliselle Arokloori 1254 PCB-seokselle. Sikiönkehityksen aikana altistuneiden jälkeläisten luuston poikkileikkausen morfologia ja biomekaaniset ominaisuudet mitattiin ja tulokset mallinnettiin vertailuannoksen määrittämiseksi. Lisäksi TCDD-altistettujen rottien luustomatriisin ominaisuuksia selvitettiin nanoindentaatiomenetelmällä. Samaa menetelmää käytettiin myös aikuisiässä TCDD:lle altistettujen villityypin hiirten ja AHR-poistogeenisiten hiirten tutkimiseen. Näiden hiirten luuston hienorakennetta mitattiin myös korkean resoluution mikro-tietokonetomografialla ja niiden luusolujen aktiivisuutta tutkittiin seerumin biomarkkerien ja luun muodostumiseen osallistuvien geenien ekspressiotasojen avulla. Sikiönkehityksen aikainen altistuminen pohjoiselle saasteseokselle ja Arokloori 1254:lle hidasti luiden pituuskasvua. Lisäksi luiden poikkileikkauspinta-alat olivat pienentyneet ja mekaaniset ominaisuudet heikentyneet. Toisaalta hohkaluun määrä oli lisääntynyt altistumisen seurauksena. Myös sikiönkehityksen aikainen altistuminen TCDD:lle hidasti luukudoksen kypsymistä ja johti aikuisiällä luukudoksen ennenaikaiseen vanhenemiseen. AHR:llä oli päärooli ainakin aikuisiän vaikutusten ilmenemiselle ja reseptorilla vaikutti olevan rooli luuston kehityksessä ylipäätään. Seerumin biomarkkereiden ja geeniekspression muutosten perusteella nämä vaikutukset johtuvat todennäköisesti luuston uusiutumisen häiriöistä. Yhteenvetona voidaan todeta, että POP-yhdisteet heikentävät luustoa, mutta tämän ilmiön diagnosoiminen on hankalaa, koska huonolaatuisen kuoriluun sisällä hohkaluun määrä on lisääntynyt.

Les polluants organiques persistants (POPs) sont des substances toxiques ayant la capacité de se bioaccumuler le long de la chaîne alimentaire. Une fois émis dans l'atmosphère, ils sont dispersés par le vent puis se déposent au sol. Du fait de leur persistance, ils peuvent être réémis depuis le sol vers l'atmosphère et parcourir ainsi de longues distances. Ce processus est couramment appelé « effet saut de sauterelle ». On peut donc retrouver les POPs très loin de leurs sources d'émissions. Pour pouvoir prendre des décisions visant à réduire leur impact environnemental, il est nécessaire de comprendre leur comportement dans l'atmosphère mais également dans les autres milieux, tels que le sol, la végétation ou l'eau. De nombreux modèles numériques de complexité variable ont été développés dans le but de prédire le devenir des POPs dans l'environnement. La plupart d'entre eux considèrent le sol comme un compartiment homogène, pouvant ainsi mener à une sous-estimation des réémissions du sol vers l'atmosphère. Or, du fait de la mise en place de réglementations visant à réduire les émissions anthropiques des POPs, la concentration dans l'atmosphère tend à diminuer et le sol, qui semblait jusqu'alors être seulement un réservoir, devient une source potentielle de POPs pour l'atmosphère. Il apparaît donc nécessaire de coupler les modèles de dispersion atmosphérique à un modèle de sol réaliste. Mes recherches ont permis d'étudier l'impact des interactions entre le sol et l'atmosphère sur la concentration dans les différents milieux. Pour cela, nous avons développé un modèle de sol multi-couches permettant de mieux estimer le profil de concentration dans le sol et les échanges entre ces deux milieux. Une analyse de sensibilité a été effectuée afin d'identifier les paramètres clés dans la détermination des réémissions. Puis ce modèle a été couplé à un modèle 3D de chimie-transport atmosphérique. Une étude de cas à l'échelle européenne a alors été réalisée afin d'évaluer ce modèle et d'estimer l'impact des réémissions sur les concentrations de POPs dans l'environnement / Persitent Organic Pollutants (POPs) are toxic substances that bioaccumulate in the food chain. Once emitted in the atmosphere, they are transported by the wind and deposited on soil. Since they are persistent, they can be reemited from soil to atmosphere by volatilization and travel over very long distances. This process is called grasshopper effect. Thus, POPs may be found at significant levels far from their emission source. It is necessary to understand the transport and fate of these pollutants in order to support the decision making process and reduce human exposure to POPs. Regulations over the last decades lead to a decrease of anthropogenic emissions and subsequent decrease of atmospheric concentration. In this context, the soil is no longer a sink of POPs but can be a source to the atmosphere. Many numeric models aim to study the behavior of POPs in the environment. Most of them consider soil compartment as a homogeneous box, leading to an underestimation of reemissions. Then, it appears of great importance to develop more realistic soil models. The objective of my thesis was to develop such a model, with vertical transport within the soil. This model was evaluated against measured concentration soil profile. We also conducted a sensitivity analysis to identify the key parameters involved in the process of reemissions. Then, the soil model was coupled with an atmospheric transport model. A case study was finally undertaken to estimate the impacts of reemissions on global-mass balance of POPs at European scale

Les estuaires sont des écosystèmes aquatiques particulièrement soumis au changement global et notamment à la pollution par de nombreux xénobiotiques pouvant présenter un risque écotoxicologique et sanitaire. En toxicologie environnementale et en évaluation des risques la bioaccumulation est un processus fondamental car elle contrôle les doses internes de toxiques potentiels. Or les flux de contamination et de décontamination des organismes dépendent de processus internes (e.g. nutrition, croissance) eux-mêmes dépendant des conditions environnementales (e.g. température, nourriture) qui peuvent être affectées par le changement global.Dans ce contexte, cette thèse se propose de décrire, dans un cadre de modélisation mécaniste, les processus de bioaccumulation de deux familles de polluants organiques persistants (POP) halogénés potentiellement toxiques et bioaccumulables, aux propriétés physico-chimiques contrastées : les polychlorobiphényles (PCB, composés historiques fortement lipophiles) et les substances perfluorées (PFAS, composés émergents amphiphiles). Ce travail se focalise sur l’estuaire de la Gironde dont la fonction de nourricerie est fondamentale pour de nombreuses espèces de poissons marins dont la sole commune (Solea solea), souvent utilisée comme indicatrice de la qualité des nourriceries côtières et estuariennes.Pour permettre de tenir compte des fluctuations des conditions environnementales sur la bioaccumulation, dans la première partie de ce travail, j’ai développé un modèle de toxicocinétique(TK) couplé avec un modèle mécaniste bioénergétique basé sur la théorie DEB (Dynamic Energy Budget). Ce modèle DEB a été paramétré pour la sole commune et calibré pour chaque sexe (package DEB tool). Il permet de prédire les principales évolutions des fonctions physiologiques d’intérêt en bioaccumulation (ingestion, croissance, reproduction...), tout au long du cycle de vie d’un individu, en fonction de conditions environnementales dynamiques. Le modèle TK développé a été complexifié par l’ajout d’un flux d’élimination de contaminants, non considéré dans les précédents modèles DEB-TK.La calibration des paramètres toxicocinétiques (TK) du modèle, pour 4 congénères de PCB, est basée sur une méthode innovante de prise en compte de la variabilité individuelle d’ingestion, appliquée à une expérimentation de contamination de juvéniles de sole via leur nourriture. Ce travail a montré que même en tenant compte de l’ingestion de chaque poisson, l’assimilation efficace de contaminant était très variable et corrélée aux taux de lipides des individus. Dans une seconde partie, ce modèle a été appliqué aux conditions in situ de l’estuaire de la Gironde. Il a permis de mettre en évidence la forte influence de la composition du régime alimentaire sur la variabilité de l’âge à la maturité sexuelle et de la contamination des soles pour les deux familles de contaminant étudiées. La confrontation des prédictions du modèle aux mesures de contaminants dans les juvéniles de sole de l’estuaire a permis de calibrer les paramètres TK du composé majeur de chaque famille dans l’environnement (CB153 et PFOS). Cette calibration a conduit à deux constats dans le cadre de l’évaluation du risque : (1) un manque de connaissances pour extrapoler les calibrations de paramètres TK en conditions contrôlées vers les conditions naturelles ; (2) la différence d’erreur d’évaluation du risque liée à l’utilisation des mêmes paramètres TK «les plus pessimistes » quels que soient les composés. Enfin, des scenarios prospectifs simples ont été développés pour illustrer ces résultats et les possibles applications du modèle développé.In fine, ces prédictions de la contamination, de la croissance et du développement des soles pourront être reliées, lors de travaux ultérieurs, à des effets potentiels sur les fonctions physiologiques de la sole (modèles DEBtox), et aux conséquences sur la dynamique des populations de soles (e.g.modèles matriciels de population). / Estuarine ecosystems are particularly impacted by global change and, specifically, bychemical pollution from numerous xenobiotics that may be associated to ecotoxicological and health risks. In environmental toxicology and risk assessment, bioaccumulation is a fundamental process as it controls the internal doses of potential toxicants in organisms. However, the contamination and decontamination flows depend on internal processes thatare themselves dependent on environmental conditions (e.g. temperature, food) and thus on the other variables of global change.In this context, this manuscript aims at describing, within a mechanistic modelling framework, the bioaccumulation processes of two families of potentially toxic and bioaccumulable halogenated persistent organic pollutants (POPs) with contrasting physicochemical properties: the polychlorinated biphenyls (PCBs, highly lipophilic historical compounds) and the perfluorinated substances (PFAS, amphiphilic emerging compounds).This work focuses on the Gironde estuary whose nursery function is fundamental for many species of marine fish including the common sole (Solea solea), often used as an indicator of the quality of coastal and estuarine bursary grounds. In order to account for the influence of environmental conditions on bioaccumulation, the first part of this work consisted in developing a toxicokinetic model (TK) coupled with a mechanistic bioenergetic model based on the theory DEB (Dynamic Energy Budget). This DEBmodel has been parameterized for common sole and calibrated for each sex (packageDEBtool). It allows predicting the main evolution of the physiological functions of interest forbioaccumulation (ingestion, growth, reproduction...) throughout the life cycle of an individualaccounting for dynamic environmental conditions. The developed TK model was first calibrated for some PCBs, under controlled conditions, using an innovative method to take into account individual ingestion variability. This work showed that even if the individual ingestion of each fish is accounted for, the effective assimilation of contaminant is very variable and correlated with the lipid levels of the individuals. The application of the model tothe in situ conditions of the Gironde estuary led to identify that, whatever the contaminant family, the composition of the soles diet had a strong influence on the variability of soles contamination and age at sexual maturity. The comparison of model predictions with measurements made in juveniles of the estuary allowed calibrating the TK parameters values for the major compound of each family in the environment (CB153 and PFOS). This calibration led to two observations in the context of a risk assessment: (1) a lack of knowledge to extrapolate calibrations of TK parameters under controlled conditions to natural conditions;(2) the difference in risk assessment error related to the use of the same "worst case" TK parameters regardless of the compounds. Lastly, simple prospective scenarios have beendeveloped to illustrate these results and the possible applications of the model developed.Ultimately, these predictions of soles contamination, growth and development may be related in future work to potential effects on the physiological functions of sole (DEBtox models), and to consequences on soles population dynamics (e.g. matrix population models).

With parts of SA in a malaria endemic area, a preventative way of fighting malaria is with the use of pesticides such as 1,1,1–Trichloro–2,2–bis(pclorophenyl) ethane, also known as DDT. DDT is listed under the persistent organic pollutants (POPs) and considered an endocrine disruptive compound (EDC) under the Stockholm Convention. SA registered an exemption to use DDT as means to fight malaria. DDT and its isomers are, however, known EDCs. Combined with their ability to persist in the environment while not being target specific motivates further studies into possible detrimental effects. The present study aimed to establish if ED was present by comparing the male reproductive organs from snails from an area currently sprayed with DDT (for malaria control) to an area not sprayed with DDT in the Limpopo Province. A possible endpoint (the penis sheath/preputium length ratio or PSPLR) was identified for the freshwater snail Bulinus tropicus. B. tropicus and sediment samples were collected from DDT–sprayed and nonsprayed areas located close together. The snails were dissected and various morphometric parameters measured. Sediments from the sites where the snails were collected were analysed for DDT using GC–MS. Statistical analysis showed significant differences in PSPLR (and therefore possible ED) between snails from the two areas. The difference in PSPLR values was mainly due to a relatively shorter preputium for the snails from the DDT–sprayed area. Even though the sediment samples showed that DDT was present in most of the DDT–sprayed sites and not in the non–DDT sprayed sites, causality of the possible ED could not be established from this field study. This study indicated the possibility of using the PSPLR as endpoint for ED. Recommendations are made for further development of the PSPLR and B. tropicus as biological indicators for endocrine disruption, but causality must first be established. / Thesis (M.Sc (Environmental Science))--North-West University, Potchefstroom Campus, 2011.

With parts of SA in a malaria endemic area, a preventative way of fighting malaria is with the use of pesticides such as 1,1,1–Trichloro–2,2–bis(pclorophenyl) ethane, also known as DDT. DDT is listed under the persistent organic pollutants (POPs) and considered an endocrine disruptive compound (EDC) under the Stockholm Convention. SA registered an exemption to use DDT as means to fight malaria. DDT and its isomers are, however, known EDCs. Combined with their ability to persist in the environment while not being target specific motivates further studies into possible detrimental effects. The present study aimed to establish if ED was present by comparing the male reproductive organs from snails from an area currently sprayed with DDT (for malaria control) to an area not sprayed with DDT in the Limpopo Province. A possible endpoint (the penis sheath/preputium length ratio or PSPLR) was identified for the freshwater snail Bulinus tropicus. B. tropicus and sediment samples were collected from DDT–sprayed and nonsprayed areas located close together. The snails were dissected and various morphometric parameters measured. Sediments from the sites where the snails were collected were analysed for DDT using GC–MS. Statistical analysis showed significant differences in PSPLR (and therefore possible ED) between snails from the two areas. The difference in PSPLR values was mainly due to a relatively shorter preputium for the snails from the DDT–sprayed area. Even though the sediment samples showed that DDT was present in most of the DDT–sprayed sites and not in the non–DDT sprayed sites, causality of the possible ED could not be established from this field study. This study indicated the possibility of using the PSPLR as endpoint for ED. Recommendations are made for further development of the PSPLR and B. tropicus as biological indicators for endocrine disruption, but causality must first be established. / Thesis (M.Sc (Environmental Science))--North-West University, Potchefstroom Campus, 2011.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Polychlorinated biphenyls (PCBs) are toxic, non-biodegradable, and lipophilic chemical compounds of industrial origin. In Brazil, PCBs are still used in old electrical transformers and capacitors which were installed up to 1981 when their use and commercialization were banned. However, the permission to use devices with PCBs installed up to the early 80s was maintained up to the moment that their dielectric fluids or the entire device be fully replaced for products free of PCBs. Currently, PCBs are classified as persistent organic pollutants (POPs) because they pollute and accumulate in the environment affecting all organisms in the food chain. The main form of human intake is the ingestion of contaminated food, especially food of animal origin. Fish are the main means of transmission of PCB congeners to the human body. The concern about PCBs is centered on their toxicological potential, especially as inducers of cancer. Thus, the aim of this study was to investigate the possible contamination by residues of 11 individual PCB congeners in fresh marine fish from the state of Rio Grande do Sul (RS), Brazil. The methodology for the analysis of PCBs in fish included sampling on the coast of RS, the extraction and purification of these compounds by the use of acidified silica gel and solvents, as well as their identification and quantification using gas chromatography coupled to a micro electron capture detector (GC - μECD). Results were confirmed by gas chromatography coupled to mass spectrometry (GC - MS). PCBs investigated were not found in all samples. PCBs 28 and 52 were not detected. PCBs 153, 138, 180, 118, 101, 77, and 81 were found in 98.33 %, 95%, 93.33%, 60%, 33.33 %, and 31.67 % of the samples, respectively. PCBs 126 and 169 were found at lower frequencies, 18.33% and 15%, respectively. The individual congeners found in higher mean concentrations were PCB 153 (184.36 ng/g fat), followed by PCB 138 (159.27 ng/g fat), PCB 118 (98.16 ng/g fat), PCB 180 (69.04 ng/g fat), PCB 101 (32.99 ng/g fat), and PCB 77 (12.95 ng/g fat). PCBs 81, 126 and 169 were found in lower concentrations (4.97 ng/g, 4.49 ng/g and 2.08 ng/g fat, respectively). Results confirm the contamination by PCBs of all marine species of consumption analyzed and can be used as indicators of environmental contamination by these compounds in the coast of RS. / Bifenilos policlorados (PCBs) são compostos químicos de origem industrial, tóxicos, não biodegradáveis, lipofílicos, e que foram produzidos a partir da década de 30 até os anos 70, quando foram proibidos. No Brasil, PCBs estão presentes, por exemplo, em transformadores e capacitores elétricos instalados até 1981, quando a comercialização e utilização desses compostos foram proibidas no país. Porém, manteve-se a permissão de utilização desses equipamentos contendo PCBs e instalados até o início dos anos 80, até que ocorra a substituição integral dos mesmos ou a troca de seus respectivos fluidos dielétricos por produtos isentos de PCBs. Atualmente, PCBs são classificados como poluentes orgânicos persistentes (POPs), pois poluem e se acumulam no meio ambiente, influenciando todos os organismos da cadeia alimentar. A principal forma de contaminação humana é a ingestão de alimentos contaminados, principalmente alimentos de origem animal. Dentre esses, os pescados constituem-se no principal meio de veiculação de congêneres de PCBs até o organismo humano. A preocupação acerca dos PCBs está centrada no seu potencial toxicológico, principalmente como indutores de câncer. Diante disso, o objetivo desse trabalho foi investigar a possível contaminação, por resíduos de 11 congêneres individuais de PCBs, em pescados marinhos in natura do estado do Rio Grande do Sul, Brasil. A metodologia empregada para análise de PCBs nos pescados incluiu a coleta de amostras do litoral do RS, a extração e purificação desses compostos com a utilização de sílica gel acidificada, solventes e, finalmente, a identificação e quantificação dos mesmos utilizando-se cromatografia gasosa acoplada a um micro detector de captura de elétrons (GC-μECD). Os resultados obtidos foram confirmados por cromatógrafo gasoso acoplado à espectrometria de massas (GC-MS). Os PCBs investigados não foram encontrados em todas as amostras analisadas. Os PCBs 28 e 52 não foram detectados. O PCB 153 foi encontrado em 98,33% das amostras analisadas, seguido pelos PCBs 138 e 180 encontrados em 95% das amostras, pelo PCB 118 encontrado em 93,33% das amostras, pelo PCB 101 encontrado em 60% das amostras, pelo PCB 77 e PCB 81, encontrados em 33,33% e 31, 67% das amostras, respectivamente. Os PCBs 126 e 169 foram encontrados com menores freqüências, 18,33% e 15%, respectivamente. Os congêneres individuais encontrados em maiores concentrações médias foram o PCB 153 (184,36 ng/g de gordura), seguido pelo PCB 138 (159,27 ng/g de gordura), PCB 118 (98,16 ng/g de gordura), PCB 180 (69,04 ng/g de gordura), PCB 101 (32,99 ng/g de gordura) e PCB 77 (12,95 ng/g de gordura). Os PCBs 81, 126 e 169 foram encontrados nas menores concentrações (4,97 ng/g, 4,49 ng/g e 2,08 ng/g de gordura, respectivamente). Os resultados obtidos confirmam a contaminação por PCBs de todas as espécies marinhas de consumo analisadas e podem ser utilizados como indicativos da contaminação ambiental, por esses compostos, no litoral do RS.

L’océan Austral est soumis à la redistribution globale des contaminants par les voies atmosphérique et océanique. Cependant, la contamination des écosystèmes austraux est très peu connue, en particulier dans le secteur Indien. De par leur toxicité, leur mobilité et leur capacité à se bioaccumuler dans les tissus des organismes et à se bioamplifier dans les réseaux trophiques, le mercure (Hg) et les polluants organiques persistants (POPs) comptent parmi les contaminants les plus préoccupants. Du fait de leur position élevée dans les réseaux trophiques, les oiseaux marins sont exposés à de grande quantités de contaminants par la voie alimentaire. En conséquence, ils sont souvent utilisés comme bioindicateurs de l’état de contamination des écosystèmes, par le biais des plumes et du sang, qui peuvent être échantillonnés de façon non destructive. Ma thèse s’est intéressée aux nombreuses espèces d’oiseaux marins (plus de 40) qui nichent au sein des Terres Australes et Antarctiques Françaises, au sud de l’Océan Indien, afin de décrire et expliquer les niveaux de contaminants le long d’un large gradient latitudinal, de l’Antarctique à la Zone Subtropicale, et d’identifier les meilleures espèces bioindicatrices pour un suivi à long terme de la contamination de ces écosystèmes. Au cours d’une première étape méthodologique, les manchots et les poussins de toutes les espèces ont été identifiés comme de bons bioindicateurs de contamination puisque, à la différence de la plupart des oiseaux adultes, ils présentent une faible variabilité des niveaux de contaminants dans les plumes. Au cours d’une seconde étape explicative, l’effet de facteurs intrinsèques (traits individuels) et extrinsèques (écologie alimentaire déduite grâce à la méthode des isotopes stables) sur les niveaux de contaminants a été évalué dans les plumes des oiseaux de la communauté de Kerguelen (27 espèces) et dans le sang du grand albatros de Crozet (180 individus dont les traits de vie sont connus). L’écologie alimentaire s’est avérée être le principal facteur explicatif des niveaux de contaminants, tandis que l’âge, le sexe, la phylogénie et le statut reproducteur jouent un rôle mineur. La classe d’âge est néanmoins un facteur à prendre en compte, puisque les poussins montrent souvent des concentrations inférieures aux adultes. Au cours d’une troisième étape, les variations spatio-temporelles de la contamination ont été étudiées en utilisant une sélection d’espèces bioindicatrices et en tenant compte de leur écologie alimentaire. Plusieurs résultats portant sur différentes espèces (oiseaux océaniques) et populations (poussins de skua) ont montré que, contrairement aux prédictions, l’exposition des oiseaux au Hg augmente graduellement des eaux antarctiques aux eaux subantarctiques puis aux subtropicales, alors que l’exposition aux POPs, en accord avec la théorie de la distillation globale, montre la tendance inverse. D’autre part, la comparaison des concentrations en Hg dans les plumes de manchot, effectuée entre des spécimens de musée et des échantillons actuels, indique que leur exposition au Hg n’a pas changée depuis les années 1950-1970. Toutefois, des espèces subantarctiques montrent une tendance à la hausse. De futures études devraient viser à l’utilisation des plumes comme tissu de référence pour l’évaluation et le suivi de la contamination des écosystèmes, en particulier en ce qui concerne les POPs. Parmi les nombreuses espèces étudiées au cours de ces travaux de thèse, les bioindicateurs les plus pertinents se révèlent être le manchot empereur et le pétrel des neiges (Antarctique), le manchot royal, le pétrel bleu et l’albatros à sourcil noirs (subantarctique), le gorfou sauteur subtropical et l’albatros à bec jaune (subtropical). Le suivi à long terme de ces espèces permettra d’évaluer l’évolution temporelle de l’état de contamination de l’océan Austral. / Antarctic and subantarctic marine environments are reached by inorganic and organic contaminants through ocean circulation and atmospheric transport. Yet, environmental contamination is poorly known in the Southern Ocean, in particular in the Indian sector. Among environmental contaminants, mercury (Hg) and persistent organic pollutants (POPs) are primarily of concern, because they are toxic, highly mobile, and they bioaccumulate in the tissues of living organisms and biomagnify up the food web. Seabirds, as upper predators, are exposed to large quantities of contaminants via food intake and have widely served as biomonitors of marine contamination, notably through the non-destructive sampling of their feathers and blood. My doctoral work has focussed on the abundant and diverse seabird species (more than 40) breeding in the French Southern and Antarctic Lands, southern Indian Ocean, in order to describe and explain contaminant concentrations over a large latitudinal gradient, from Antarctica to the subtropics, and to identify the best bioindicator species for contaminant biomonitoring. In a first methodological step, seabirds with synchronous moult of body feathers (adult penguins and chicks of all species) were recognised as good candidates as bioindicators, because, unlike most adult birds, they present low within-individual variation in feather contaminant concentrations. In a second explanatory step, the influence of intrinsic (individual traits) and extrinsic factors (feeding ecology inferred from the stable isotope method) driving variation in contaminant concentrations was evaluated in feathers of the large avian community of the Kerguelen Islands (27 species) and in blood of wandering albatrosses from the Crozet Islands (180 birds of known individual traits). Feeding ecology was the main factor driving variation in contaminant concentrations of blood and feathers, both at the community, population and individual levels, whereas age, sex, phylogeny and breeding status played a minor role. Age-class was however an important intrinsic factor to consider, with chicks usually having lower concentrations than adults. In a third step, spatio-temporal patterns of contamination were studied through selected bioindicator species and by taking into account their feeding habits. Results from different species (oceanic seabirds) and populations (skua chicks) showed that, contrary to predictions, Hg exposure gradually increases from Antarctic to subantarctic and subtropical waters, whereas, in accordance with the global distillation theory, POPs exposure has the opposite pattern. Comparisons between penguin feathers from museum collections and contemporary samples showed that bird exposure to Hg is overall not different today when compared to 50-70 years ago, but subantarctic species are possibly experiencing an increasing trend. Future research efforts should be focussed on the use of feathers as biomonitoring tools, in particular for POPs determination. The best recommended bioindicator species include the emperor penguin and snow petrel (Antarctic), king penguin, blue petrel and black-browed albatross (subantarctic), and northern rockhopper penguin and Indian yellow-nosed albatross (subtropical). Future biomonitoring studies on these species will give invaluable insights into the poorly-known temporal trends of environmental contamination in the Southern Ocean.