Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2018-02-08T13:16:32Z No. of bitstreams: 1 Dissertação Monteiro.pdf: 846441 bytes, checksum: b2f2bba3715f02d6517b44747e771a73 (MD5) / Made available in DSpace on 2018-02-08T13:16:32Z (GMT). No. of bitstreams: 1 Dissertação Monteiro.pdf: 846441 bytes, checksum: b2f2bba3715f02d6517b44747e771a73 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / Este trabalho tem como objetivo estudar o aporte dos metais-traço Pb, Zn, Ni, Cu, V, Ba, Co, Cd em sedimentos do estuário do Rio Iguaçu e da região da Área de Proteção Ambiental de Guapimirim, comparando o grau de acumulação destes metais nestes diferentes ambientes estudados. Para isso, foram coletados dois testemunhos de sedimentos, um na margem deposicional do Rio Iguaçu (RED3) e o outro entre as fozes dos rios Guapi e Guarai (MAC), na Baía de Guanabara. O testemunho RED3 apresentou sedimentos com granulometria predominantemente composta por argila e silte, com máximo de areia de 3%, enquanto o testemunho MAC também apresentou granulometria fina, porém este apresentou até 20% de areia em algumas camadas sedimentares. Ambos os testemunhos mostraram mudanças nas taxas de sedimentação a partir da segunda metade do século XX, refletindo o início do acelerado processo de urbanização da área metropolitana do Rio de Janeiro. As concentrações de carbono orgânico, metais-traço, Fe e Mn determinados nos sedimentos do testemunho RED3 oscilaram ao longo de todo testemunho, sugerindo uma elevada dinâmica do Rio Iguaçu. Foi verificado um incremento na concentração de todos os metais-traço, Fe e Mn por volta de 1987, sugerindo uma redistribuição diagenética dos metais. Já o perfil de concentração dos metais-traço determinados no testemunho MAC mostraram dois períodos de valores de background. O primeiro é da base até 75 cm de profundidade (equivalente ao ano de 1872), mostrando um ambiente deposicional com predominância de argila, matéria orgânica alóctone e baixos valores de concentração de metais-traço. Acima desta profundidade ocorreu um progressivo incremento nas concentrações dos metais, com alguns metais chegando a dobrar suas concentrações, e a partir daí mantendo-se relativamente constantes até a superfície (com exceção do Zn e Pb). Estes incrementos provavelmente foram influenciados pelas novas condições ambientais da bacia de drenagem do final do século XIX, possivelmente devido ao processo de desmatamento, ocasionando assim uma maior erosão e intemperismo do solo. Os resultados dos inventários, fluxos e fatores de enriquecimento dos metais-traço tanto se mostraram mais elevados na região do Rio Iguaçu do que na área de proteção ambiental, quanto nos demais importantes estuários mundial. / The aim of the present work is to study the input of trace metals of environmental interest, such as Pb, Zn, Ni, Cu, V, Ba, Co e Cd, in sediments from the Iguaçu River and the Guapimirim Environmental Protection Area estuaries, comparing the degrees of metal accumulation between these environments. Two sediment cores were collected in 2007, one from the mudflat inside the Iguaçu River (RED3) and the other near the Guapi and Guarai river mouths (MAC). The sediment core RED3 presented sediments predominately composed for silte and clay, with a maximum sand content of 3%. The sediment core MAC also presented fine granulometric size, however it showed up to 20% of sand in some sedimentary layers. Both sediment cores showed a change in sedimentation rates from the second half of the twentieth century, which might be reflecting the beginning of an accelerated industrialization process and development of the Rio de Janeiro Metropolitan Area. The sediment core RED3 presented a large concentration variation of organic carbon, trace metals, Fe and Mn. This might be a reflection of the high Iguaçu River hydrodynamic. All the trace metals, Fe and Mn presented a concentration increase in the second half of the 1980’s, suggesting a vertical redistribution due the process diagenetic. The trace metal concentration found in the MAC core showed two background levels. The first level consists of concentrations measured from the core bottom up to 75 cm, which was equivalent to records up to 1872. Moreover, the sediments from those environmental conditions predominantly presented clay, aloctone organic matter and low concentrations of trace metals. From the mentioned depth onwards, there were concentration increases. Once increased, the concentration remained constant until the top of the core (except Zn and Pb). These increases were probably influenced by the new environmental conditions catchment in the end of XIX century, possibly due to a deforestation process, which occasioned major erosion and weathering. Inventory, flux and trace metal enrichment factors showed highest in the Iguaçu River than in the Guapimirim Environmental Protection Area other estuaries and the others important estuaries of the world.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / This study addresses the distribution of trace metals in sediment cores from the dam Marcela in order to evaluate the occurrence of impacts associated with human and industrial activity. The dam is located in the city Itabaiana in the state of Sergipe, it was built in the period 1953 - 1957 barring Fuzil stream. It has an area of 1.4 km2 with storage capacity of 2,700,000 m3. Two sediment cores were collected in November of 2008 with approximately 45cm in two distinct points. The samples were sectioned in 5 cm each and they were analyzed by to determine the following chemical elements: Co, Cr, Cu, Ni, Pb, Zn, Mn, Al, Fe, Corg and Ntotal. The average value of Corg/Ntotal in the range 4,97- 7,64 and 6,39-7,69, for cores I and II respectively, indicative autochthonous and allochthonous origin of the organic matter. The multivariate statistical analysis (Principal component analysis) applied to the set of results showed that the two cores in relation to concentrations of metals are different, with evidence of enrichment for Cr, Cu, Mn and Zn in the surface layers. The contamination factor calculed showed contamination moderate level for metals Cr, Cu, Mn and Zn. The risk assessment code (RAC), which consider the percentage of metal extracted in the label fraction (F1) of BCR procedure, showed that chromium does not present risk to the environment, copper, nickel and lead were low to medium risk, and zinc had of very high to High risk to the aquatic environment. Small variations in environmental conditions, such as pH or salinity, could therefore increase availability of the elements to the aquatic system. The metals concentrations were always at the lower limit the TEC and PEC, defined by consensual sediment quality guidelines (SQGs), in this case, it is not possible to predict what adverse effects the metal can cause in this environment. / Neste trabalho foi determinada a distribuição de metais traço em testemunhos de sedimento do Açude Marcela com o objetivo de avaliar a ocorrência de impactos associados à atividade humana e industrial, desenvolvidas naquela região. O Açude Marcela localiza-se na cidade de Itabaiana Sergipe, foi construído no período 1953 à 1957 pelo barramento do riacho Fuzil e tem uma área de 1,4km2 , com capacidade de armazenamento de 2.700.000 m3. Foram coletados em novembro de 2008 dois testemunhos de sedimentos com aproximadamente 45cm de profundidade em dois pontos distintos do açude. Os testemunhos foram secionados a cada 5cm para determinação dos seguintes elementos químicos: Co, Cr, Cu, Ni, Pb, Zn, Mn, Al, Fe, Corg e Ntotal. A relação Corg/Ntotal variou de 4,97-7,64 e 6,39-7,69 para os testemunhos I e II, respectivamente, indicando origem autóctone e alóctone para a matéria orgânica presente no sedimento. A análise estatística multivariada (análise de componentes principais-ACP), aplicada ao conjunto dos resultados, mostrou que os dois testemunhos, em relação às concentrações dos metais, são estatisticamente diferentes, com evidências de enriquecimento por Cr, Cu, Mn e Zn, nas camadas mais superficiais. O fator de contaminação calculado mostrou um nível de contaminação moderado para os metais Cr, Cu, Mn e Zn. O Fator de Risco (RAC), que compreende a percentagem do metal extraída na fração lábil (F1) do procedimento (BCR) empregado, indicou que o cromo não apresentou risco ao ambiente. Cobre, níquel e chumbo apresentaram risco baixo a médio, e zinco apresentou risco alto a altíssimo para o ambiente aquático. Sendo assim, pequenas variações nas condições ambientais podem remobilizar esses elementos do sedimento para a coluna d água. As concentrações dos metais nos testemunhos estiveram entre TEC e o PEC, definidos pelos valores guias de qualidade de sedimento consensual (VGQS), indicando que, nas condições atuais, o sedimento pode exercer efeito adverso aos organismos do açude em questão.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2016-04-14T16:10:05Z No. of bitstreams: 1 Dissertação - Aline Soares Freire - FINAL.pdf: 4503064 bytes, checksum: 1e469a75225eda50cf3c49c6ab32c87a (MD5) / Made available in DSpace on 2016-04-14T16:10:05Z (GMT). No. of bitstreams: 1 Dissertação - Aline Soares Freire - FINAL.pdf: 4503064 bytes, checksum: 1e469a75225eda50cf3c49c6ab32c87a (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências-Geoquímica. Niterói, RJ / A análise de amostras hipersalinas ainda é um problema analítico a ser resolvido, tendo em vista que a presença de sais dissolvidos é fonte freqüente de interferências em espectrometria atômica. Atualmente, tem ocorrido um grande aumento da demanda para caracterização de águas de alta salinidade, como as águas produzidas, pelo fato de estas serem um dos maiores descartes da indústria de petróleo. Devido a isto, metodologias analíticas para sua caracterização têm sido amplamente desenvolvidas para a determinação de metais-traço em amostras salinas e dentre as técnicas analíticas destaca-se a Espectrometria de Absorção Atômica de Alta Resolução com Fonte Contínua, uma renovação da AAS convencional. Contudo, para a obtenção de resultados acurados, é imprescindível que se faça a remoção dos sais presentes nessas matrizes hipersalinas. Essa separação prévia pode ser realizada através do emprego de resinas qualantes, que pré-concentram o analito e permitem a remoção da matriz. Sendo assim, este trabalho visa à avaliação do uso da resina quelante comercial Chelex-100® na préconcentração de Co, Cu, Mn, Ni e Pb e posterior determinação destes por Espectrometria de Absorção Atômica de Alta Resolução com Fonte Contínua e Forno de Grafite (HR-CS GF AAS). A metodologia foi validada através do uso dos materiais de referência certificados para água do mar CASS-4, CASS-5 e NASS-5. Os limites de detecção obtidos, em μg L-1, foram de 0,006; 0,070; 0,024; 0,074; e 0,018 para Co, Cu, Mn, Ni e Pb, respectivamente. Amostras de água produzida oriundas de plataformas de petróleo offshore foram analisadas e os resultados mostraram que essas águas possuem baixas concentrações dos elementos determinados ou os mesmos não foram detectados. Os valores encontrados são muito inferiores aos limites preconizados pela legislação brasileira através da Resolução CONAMA 357/05 / The analysis of hypersaline samples is still an analytical problem to be solved, once the presence of dissolved salts is a frequent source of interferences in atomic spectrometry. Actually, there is a large increase in the interest in the caracterization of this kind of sample, as produced waters are one of the largest discharges of petroleum industry. Hence, analytical methodologies to produced water caracterization have been widely developed to trace metals determination in saline samples and among the analytical techniques, there is High Resolution Continuum Source Atomic Absorption Spectrometry, a renovation of conventional AAS. However, to obtain accurated results, it's necessary to remove the salts present in this high salinity matrices. This previous separation can be done employing a chelating resin, that preconcentrates the analyte(s) and allows matrix removal. In this way, the aim this work is to evaluate the use of chelating resin Chelex-100® to preconcentrate Co, Cu, Mn, Ni and Pb, for the later determination by High Resolution Continuum Source Graphite Furnace Atomic Absorption Spectrometry (HR-CS GF AAS). The methodology was validated by the use of sewater certified reference materials CASS-4, CASS-5 e NASS-5. The detection limits in μg L-1, were 0,006; 0,070; 0,024; 0,074; and 0,018 for Co, Cu, Mn, Ni and Pb, respectively. Produced water samples from offshore petroleum platforms were analysed and results showed that this waters have low concentrations of these studied elements or could not be detected. Found values are much lower when compared to limits from Brazilian legislation, in this case CONAMA 357/05 Resolution

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2016-04-28T18:18:17Z No. of bitstreams: 1 Tese Clarissa Lourenço de Araujo.pdf: 7002934 bytes, checksum: 52d368f8ad6a751f994f7846928d0854 (MD5) / Made available in DSpace on 2016-04-28T18:18:17Z (GMT). No. of bitstreams: 1 Tese Clarissa Lourenço de Araujo.pdf: 7002934 bytes, checksum: 52d368f8ad6a751f994f7846928d0854 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências-Geoquímica. Niterói, RJ / Este estudo teve como objetivo contribuir para caracterização do processo de incorporação biológica de metais por duas espécies fitobentônicas, a macroalga Ulva sp. e a macrófita aquática Ruppia maritima, para subsidiar futuras atividades de monitoramento da contaminação da biota aquática da Lagoa Rodrigo de Freitas por metais, bem como de outros sistemas costeiros com condições semelhantes. Este estudo baseou-se na realização de experimentos laboratoriais com o radiotraçador 51Cr (nas formas tri e hexavalente) e com Cr, Cu, Hg, Mn, Pb e Zn, para caracterizar a cinética de incorporação destes pelas duas espécies fitobentônicas. As amostras coletadas na Lagoa Rodrigo de Freitas, foram aclimatadas em laboratório e posteriormente submetidas a experimentos onde foram simuladas condições de mistura de águas salinas e fluviais com água marinha artificial de salinidades 7, 15 e 21‰ e de eventos de aumento dos níveis de matéria orgânica na coluna d’água através da adição de ácidos húmicos. A fim de elucidar os processos de sorção e incorporação de metais foram aplicadas ainda, técnicas de remoção de biofilme e de limpeza do material biológico em solução de EDTA. Nos ensaios com 51Cr (III e IV) foi observada que acumulação do metal por Ulva sp. possui relação inversa com a salinidade, enquanto para R. maritima, o máximo de acumulação ocorre em salinidade 21‰. Nos experimentos com adição simultânea de metais foi observada a seguinte ordem de abundância Pb>Zn>Hg>Cu>Mn>Cr. A maior acumulação dos metais foi observada em salinidade 15‰, com exceção apenas do Hg que apresentou máximo de incorporação em salinidade 21% para alga. Nos ensaios com adição de substâncias húmicas foi evidenciada a redução da incorporação de Cu, Pb e Zn por ambas espécies. No tocante ao potencial de acumulação, foi verificada a maior habilidade de sorção de metais por Ulva sp., independentemente da faixa de salinidade aplicada. Nos ensaios de remoção do biofilme aderido a R. maritima foi observada a redução das concentrações de Cu, Mn e Pb, reforçando o papel deste componente na acumulação de íons metálicos por macrófitas aquáticas. Por fim, no ensaio em que o material biológico foi lavado em solução de EDTA, foi observada a tendência de adsorção superficial de Cu, Mn e Pb, enquanto Cr e Zn, são rapidamente internalizados nos tecidos da macrófita. / This study aims to contribute to the characterization of the process of biological incorporation of metals by two benthonic species, the macroalgae Ulva sp. and the aquatic macrophyte Ruppia maritima, to subsidize future activities of monitoring the contamination of aquatic biota of the Rodrido de Freitas Lagoon for metals, as well as other coastal systems with similar conditions. This study was based on laboratory experiments with the radiotracer 51Cr (in forms tri and hexavalent) and with Cr, Cu, Hg, Mn, Pb and to characterize the kinetics of incorporation of these by two phytobentic species. Samples collected in the Rodrigo de Freitas Lagoon were acclimated in the laboratory and subsequently subjected to experiments where conditions of saline and river water mixed with artificial marine water with salinities of 7, 15 and 21‰ were simulated as well as events that increase the levels of organic matter in the water column through the addition of humic acids. In order to elucidate the processes of sorption and incorporation of metals, techniques for the removal of biofilm and the cleaning of biological material in EDTA solution were also applied. In tests with 51Cr (III and IV) it was observed that accumulation of the metal in Ulva sp. has inverse relationship with salinity, while for R. maritima, the maximum accumulation occurs in salinity 21 ‰. In the experiments with simultaneous addition of metals, the following order of abundance was observed Pb>Zn>Hg>Cu>Mn>Cr. The higher accumulation of metals was observed in salinity 15 ‰, with the exception of Hg that showed maximum incorporation in salinity 21% for algae. In tests with addition of humic substances, the reduction in the incorporation of Cu, Pb and Zn both species was evidenced. In regards to the potential for accumulation, it was verified the greater capability of sorption of metals by Ulva sp., regardless of range of salinity applied. In tests of removal of biofilm attached to R. maritima, the reduction of concentrations of Cu, Mn and Pb was observed, reinforcing the role of this component in the accumulation of metal ions by aquatic macrophytes. Finally, in the biological test material that was washed in EDTA solution, the tendency of surface adsorption of Cu, Mn and Pb was observed, while Cr and Zn are rapidly internalized in the tissues of macrophyte.

No description available.

D. Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology / A novel low-cost ternary Mn-Fe-Cu (MFC) metal oxide nanocomposite adsorbent was fabricated using facile co-precipitation method and successfully applied for the sequestration of Cr(VI) and As(III) from simulated aqueous efflent. The central composite design (CCD) of the response surface methodology (RSM) optimization technique determined the optimal working parameters for the preparation of the ternary MFC metal oxide nanocomposite. The spectroscopic microstructural analysis of the ternary MFC metal oxide nanocomposite was performed using fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) spectroscopy. The spectroscopic analyses revealed a rough surface with hydroxyl groups and the presence of mixed metal oxides in different valence states. The BET surface area, pore volume and pore size of the nanostructured MFC ternary metal oxide composite were found to be 77.2427 m2/g, 0.2409 cm3/g and 14.7560 nm, respectively. The pH drift method determined that the pHpzc of the adsorbent was 6.75. The batch technique was employed to investigate the adsorption dynamics (effects of ionic strength, co-existing anions, adsorbent regeneration and reuse) and optimum parameters (solution pH, adsorbent dosage concentration, desorption) of Cr(VI) and As(III) adsorption onto the MFC nanocomposite. The fitting of non-linear kinetic (pseudo-first-order, pseudo-second-order and Elovich), diffusion (intraparticle and Boyd) and isotherm (Langmuir, Freundlich and Dubinin-Radushkevich) models to the Cr(VI) and As(III) experimental adsorption data gave an insight into the adsorption mechanisms. The Langmuir adsorption capacities, qm (mg/g), were 168.71 at solution pH 3 and 35.07 at solution pH 9 for Cr(VI) and As(III) adsorption, respectively. The adsorption of Cr(VI) onto the ternary MFC metal oxide nanocomposite was physical and formed outer-sphere surface complexes through electrostatic interactions, while the removal of As(III) was specific due to inner-sphere surface complexation and ligand/ion exchange reactions. The results from XPS and FTIR analysis after the adsorption of Cr(VI) and As(III) showed that the surface hydroxyl groups on the MFC nanocomposite interacted with the Cr(VI) and As(III) species during the formation of the surface complexes. To facilitate ease of adsorbent removal from the treated simulated aqueous effluent, the ternary MFC metal oxide system was co-precipitated onto biochar support.

Recently, the agricultural, industrial and mining activities have led to increase in contaminant emission. Trace metals or herbicides are among the pollutants to be concerned in the world. In this study we evaluated the effects of the herbicide atrazine (at the concentrations of 5, 50 and500 µg L-1) and its combination with copper (Cu, 50 µg L-1) and chromium (Cr, 50 µg L-1) on duckweed over the period of 10 days in the laboratory conditions. We found that 50 and 500 µg atrazine L-1 severely impacted on the growth or even caused the death of the plants, whereas there was no statistically significant difference in the duckweed growth rate between the 5 µg atrazine L-1 exposure and control. In the combined treatments (50 µg atrazine L-1 with Cu; with Cr or with both Cu and Cr), the plant growth rate of atrazine with either Cu or Cr was strongly reduced. However, the mixture of atrazine with Cu and Cr did not significantly decrease the development and growth rate of duckweed. Besides, atrazine and investigated heavy metals resulted in turning whiteof duckweek leaves that evidence ofthe chlorophyll degradation. Our results showed the negative influences of the herbicide atrazine and metals on development and morphology of duckweed. / Gần đây, những hoạt động nông nghiệp, công nghiệp và khai khoáng đã và đang dẫn đến sự gia tăng phát thải các chất gây ô nhiễm. Kim loại nặng hoặc thuốc diệt cỏ là những chất gây ô nhiễm đang được quan tâm trên thế giới. Trong nghiên cứu này, chúng tôi đánh giá ảnh hưởng của thuốc diệt cỏ atrazine (nồng độ 5, 50 và 500 µg/L) và sự kết hợp của chất này với đồng (Cu, 50 µg/L) và crom (Cr, 50 µg/L) lên bèo tấm trong thời gian 10 ngày trongđiều kiện phòng thí nghiệm. Chúng tôi nhận thấy atrazine tại nồng độ 50 và 500 µg/L đã gây nên những ảnh hưởng nghiêm trọng lên sự phát triển hay thậm chí làm cho bèo tấm bị chết, trong khi đó, không ghi nhận được bất kì sự khác biệt có ý nghĩa thống kê về tốc độ tăng trưởng của bèo tấm giữa lô thí nghiệm phơi nhiễm 5 µg atrazine / L và lô đối chứng. Trong những lô phơi nhiễm kết hợp (50 µg atrazine / L với Cu, với Cr hoặc với đồng thời Cu và Cr), tốc độ tăng trưởng của bèo tấm khi phơi nhiễm với atrazine và Cu hoặc Cr bị giảm mạnh, tuy nhiên, việc phơi nhiễm đồng thời atrazine với Cu và Cr đã không làm giảm đáng kể sự phát triển và tốc độ tăng trưởng của bèo tấm. Bên cạnh đó, atrazine và kim loại nặng đã làm cho màu của lá bèo tấm chuyển sang màu trắng, điều này chứng tỏ có sự suy giảm chlorophyll. Kết quả nghiên cứu này đã cho thấy những ảnh hưởng tiêu cựccủa thuốc diệt cỏ atrazine và kim loại lên sự phát triển và hình thái của bèo tấm.

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Ce projet de recherche porte sur l’étude de la contamination de la côte libanaise par les composés organiques (HAP, DDE) et par les éléments-trace métalliques (Hg, Pb principalement). Les travaux sur les compartiments sédimentaires et biologiques de la côte libanaise constituent deux parties aux problématiques et aux approches distinctes autour desquelles s’articule cette thèse. Dans la première partie, l’analyse d’une carotte sédimentaire datée prélevée sur le plateau continental du Sud du Liban a permis de reconstituer l’historique de contamination dans le bassin Levantin. Les analyses de contaminants dans les sédiments de la carotte C1 combinés à la datation aux 210Pb et 137Cs ont permis d’obtenir un enregistrement fiable des variations du dépôt de mercure, de plomb et de HAP sur le plateau continental libanais, dans le bassin Levantin. Bien que les concentrations et les flux soient relativement faibles, une augmentation en deux phases des concentrations est bien mise en évidence par le profil sédimentaire de C1. Le charbon est identifié comme source principale de Pb, de Hg et de HAP dans le bassin Levantin entre la moitié du 19ème siècle et la moitié du 20ème siècle. Les résultats des ratios isotopiques du Pb et des ratios diagnostiques de HAP appuient ce constat. Les archives sédimentaires dans la carotte C1 fournissent un signal du dépôt de contaminants à l’échelle globale probablement lié aux sources d’émissions atmosphériques en provenance d’Europe Centrale et de l’Est. Dans la seconde partie, une étude de la contamination par les HAP du littoral libanais est menée suite à la marée noire résultant du conflit armé israélo-libanais en 2006. Une approche de biomonitoring sur trois ans utilisant l’espèce de moules invasives Brachidontes variabilis a été développée. Les résultats indiquent une décroissance progressive des concentrations de HAP dans l’écosystème intertidal du littoral libanais. La contamination par les HAP du fioul en zone subtidale en 2007 est nettement plus faible. Cependant la signature des HAP dans les tissus de moules prélevées trois ans après la marée noire indique toujours la présence des composés du fioul de Jiyeh. La contamination est particulièrement persistante dans certaines zones fortement touchées par la nappe de fioul en 2006. Il apparaît que l’état initial pré-marée noire n’a pas été atteint, même trois ans après la marée noire de Jiyeh. L’examen détaillé de l’évolution spatiale et temporelle de la contamination par les HAP de l’environnement intertidal est présenté dans ce volet de notre étude. / This research project aims at the study of the contamination of the Lebanese coast by PAHs, DDE, Hg and Pb. The research work is divided into two distinct parts concerning two environmental compartments (sedimentary and biological) and it addresses different questions and approaches. In the first part, the study of a dated sediment core raised from the continental shelf in southern Lebanese coast allowed reconstructing the contamination history in the Levantine basin. The contaminants’ analysis as well as 210Pb and 137Cs datation allowed obtaining a reliable record of mercury, lead and PAHs sedimentary deposition in the Lebanese continental margin in the Levantine basin. Although concentrations and fluxes are relatively low, a two-phase increase of concentration is found using C1 core sedimentary profiles. Coal was identified as the main source of Pb, Hg and PAHs in the Levantine basin between the mid 19th and the mid 20th century. Ratios of Pb stable isotopes and PAH diagnostic ratios support this assumption. The studied sedimentary archives provide also information on the deposition of contaminants on a global scale possibly related to atmospheric emissions mainly from Central and Eastern Europe. In the second part of the thesis, the study of contamination by PAHs of the Lebanese coast was undertaken following an oil spill in the south of Lebanon, which occurred after the bombardment by the Israeli military of the electric power plant in Jiyeh in 2006. We have set-up a biomonitoring program with an invasive mussel specie Brachidontes variabilis over a three-year study. Results indicate a progressive decrease of PAH concentrations in the intertidal ecosystem of the Lebanese coast. Contamination of the subtidal zone in 2007 by Jiyeh fuel oil was significantly lower. However, Jiyeh fuel oil signature was still detectable in mussel tissues even three years after the oil spill. Contamination was found to be particularly persistent in some of the highly oiled sites. It appears that pre-spill state was still not reached even three years following the oil spill. Detailed investigation of spatio-temporal changes of intertidal mussels contamination by PAH is also presented in this part of the thesis.

Depuis au moins 2000 ans, le massif des Vosges a été le siège d’activités minières qui ont conduit (i) à l’émission de particules contaminées en éléments traces métalliques (ETMs), (ii) aux dépôts de déchets miniers et sidérurgiques et (iii) à des modifications du paysage. Les ressources présentes dans ce système de moyenne montagne, et utilisées par les populations, rendent nécessaire la mesure des impacts des activités anthropiques passées sur l’écosystème forestier.Ce travail de thèse propose une approche multi-proxy couplant géochimie, palynologie et écotoxicologie. Différentes phases de dépôts en ETMs ont été retracées sur les 2000 dernières années et regroupent celles connues à l’échelle de l’hémisphère Nord et des phases plus locales. L’impact paysager des activités minières semble quant à lui réduit par rapport à ce que laissaient penser les archives historiques qui présentaient des déserts forestiers dus aux activités minières. La biodisponibilité et le risque associés au transfert des ETMs ont été évalués dans un ancien district minier de production de plomb (Pb) et d’argent grâce à une campagne de bioindication active avec un indicateur de la qualité des sols, Cantareus aspersus. Sur huit stations, quatre présentent des excès de transfert induisant un risque toxicologique élevé et comprennent deux sites archéologiques miniers et un potager communal. Le fractionnement et la spéciation du Pb permettent de montrer une pratique à risque avec l’utilisation de scories comme amendements sur le potager. La contamination du milieu en ETMs par les activités minières est ici toujours transférable aux organismes du sol et donc potentiellement dans le réseau trophique / Since at least the last two millennia, mining and smelting activities have occurred in the Vosges Mountains and conducted to (i) the emission of trace metal (TM) contaminated particles in the atmosphere, (ii) the presence of mining and smelting wastes and (iii) landscape changes. Due to the use of resources from this mountainous area by local populations, it is necessary to measure impacts of these past activities on the forested ecosystem.This PhD thesis proposes a multi-proxy approach coupling geochemistry, palynology and ecotoxicology. Several phases of TM deposits have been recorded and correspond to major phases of TM contamination known in the northern hemisphere and also local periods of mining/smelting activities. The impact of mining activities on the landscape appears to be reduced contrary to historical data that described shortage of wood due to mining activities. The bioavailability and the risk associated to TMs from mining activities have been assessed in a former lead (Pb)-silver mining district by an active bioindication campaign using Cantareus aspersus, considered as indicator of soil quality. Among the eight stations, four of them present an excess of TM transfer conducting to a high ecological risk, particularly in two archaeological mining sites but also in a kitchen garden. Lead fractionation and speciation highlight the use of slags as amendments in the kitchen garden. Trace metal contamination of the soil due to mining activities is still bioavailable for soil organisms and so potentially transferred in food chain.