The research work is directed towards the investigation, optimization and application of some plant-based waste materials for the removal of some toxic trace metals (Cd, Pb and Mn) as well as selected oxyhalides (CIO3-,IO3- and BrO3-) in aqueous system. Waste materials from three plants; Athrixia philicoide, an indigenous bush tea; the outer covering peels of butternut Squash (Cucurbita Moschata) and pineapple (Ananas comosus) were evaluated for their sorption efficiency of the selected metals. batch and continuous experimental processes as well as conditions that might influence the sorption of the metals were investigated. These conditions include effects of pH sorption time, amount of adsorbent, volume of the aqueous medium, amount of metals etc. Qualitative and quantitative analysis of metal ions in solution was carried out using the ion chromatograph (IC) while the functional group identification present in waste materials was established using the Fourier Transform infr-red spectroscopy (FTIR), Quantitative biosorption equilibrium of 98.99% was reached within 6h at pH 6 and 100 ppm concentration of Pb metal with Athrixiaphilicoide under 30 min contact time. Applicability of the sorption process was tested on wastewater. Results revealed that > 99.93 %; 84.5 % and 64.3 % sorption efficiency was obtained for Mn, Cd and Pb respectively at pH 7 using Ananas Comosus adsorbent. For Athrixia philicoide, sorption efficiency from spiked wastewater ranged from 99.98 % for Cd; 99.96 % for Mn and 82.5 % adsorption for Pb at pH 7. For Juglans Cinerea, wastewater sorption efficiency varied between 78.76 %, 94.50 % and 96.50 % for Cd, Mn and Pb respectively at pH6. Results from the optimized method revealed the applicability of the method to environmental water samples. Possible large scale and industrial/commercial application of developed materials and methods would be explored. ) in aqueous system. Waste materials from three plants; Athrixia philicoide, an indigenous bush tea; the outer covering peels of butternut Squash (Cucurbita Moschata) and pineapple (Ananas comosus) were evaluated for their sorption efficiency of the selected metals. Batch and continuous experimental processes as well as conditions that might influence the sorption of the metals were investigated. These conditions include effects of pH, sorption time, amount of adsorbent, volume of the aqueous medium, amount of metals etc. Qualitative and quantitative analysis of metal ions in solution was carried out using the ion chromatograph (IC) while the functional group identification present in waste materials was established using the Fourier Transform infra-red spectroscopy (FTIR). Quantitative biosorption equilibrium of 96.99 % was reached within 6h at pH 6 and 100 ppm concentration of Pb metal with Athrixia philicoide under 30 min contact time. Cd and Mn adsorption by the same adsorbent under similar condition were less than 50 % for individual metal evaluation experiment. However, > 99 % adsorption was achieved with Cd in a mixture of the three (3) evaluated metals. Highest adsorption of 93 % of Pb was achieved with the Butternut Squash peel (Cucurbita moschata) at the optimal sorption pH of 6 followed by quantitative sorption of 99.2 % of Mn while Cd recorded a sorption level of 45 % all at 6 pH. The sorption efficiency of Pb, Cd and Mn using pineapple peels (Ananas comosus) also at the optimal sorption conditions of (pH 6, 30 min contact time and 100 ppm metal concentration) ranged from 98.7 %, 100 % and 99.90 % respectively. / Enviromental Science / M.Sc (Enviromental Science)

Made available in DSpace on 2015-05-14T13:21:50Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2097791 bytes, checksum: ca496bec445fdfe57f7800a142dda529 (MD5) Previous issue date: 2010-10-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Due to the intense activity in the textile business Piranhas River, which traverses the city of São Bento-PB is serving as the depletion for the waste generated in the steps of bleaching and dyeing of yarn, since the networks are made by artisans, many them in the backyards of residences. On this context, for this work, we collected water and sediment samples at three different points of the Piranhas, with the objective to evaluate a possible contamination of these compartments resulting from dumping of textile effluent. Were also determined the variables Dissolved Oxygen (DO), Total Dissolved Solids (TDS), OM (Organic Matter), Conductivity, pH and temperature. The results obtained for these parameters are consistent with those expected for the location of the environment under study, where the rainfall is marked by extreme irregularity. An analysis screening using the voltammetry technique was used to indicate the presence of trace metals in water, this analysis showed the possible presence of metals, Zn, Pb and Cu. Concerning the sediment samples, the quantitative analysis performed using the technique of ICP-MS (Inductively Coupled Plasma-Mass Spectrometry) showed that among the investigated metals, Cd, Pb, Cu, Cr, Ni, Cr and Ni elements were those with higher levels during the study period. Using parameters of the sediment quality evaluators, it was observed that the metals Cr and Ni had values that exceeded the lower limit TEL (Canadian guideline value) thus indicating a deleterious made occasional on aquatic biota of the environment under study. Principal components analysis (PCA) using variables such as the physical-chemical parameters and concentrations of metals investigated, highlighted the influence of parameters and STD Conductivity, pH and organic matter in the grouping of data and also showed that the differences in metal contents between months in the study (rainy and dry) were more relevant than the differences between the sampling sites investigated. From the results and taking into account the variables measured along the river, it was found that there is no evidence that the textile wastewater at the moment, is affecting the characteristics of the Piranhas. / Devido à intensa atividade no ramo têxtil o Rio Piranhas, que atravessa o município de São Bento- PB, está servindo como esgotamento para os resíduos gerados nas etapas de branqueamento e tingimento dos fios, uma vez que as redes são fabricadas de maneira artesanal, muitas delas nos quintais das residências. Neste contexto, para este trabalho, foram coletadas amostras de água e sedimento em três pontos distintos do Rio Piranhas, com o objetivo de avaliar uma possível contaminação desses compartimentos resultante do despejo do efluente têxtil. Também foram determinadas os parâmetros físico-químicos oxigênio dissolvido (O.D), sólidos totais dissolvidos (STD), matéria orgânica (M.O), condutividade, pH e temperatura. Os resultados obtidos para estes parâmetros estão de acordo com os esperados para a localização do ambiente em estudo, onde o regime pluviométrico é marcado por extrema irregularidade. Uma análise qualitativa utilizando a técnica de voltametria foi realizada para indicar a presença de metais traço na água, essa análise mostrou a possível presença dos metais Zn, Pb e Cu. Em relação às amostras de sedimento, a análise quantitativa realizada através da técnica de espectrometria de massa com plasma indutivamente acoplado (ICP-MS), mostrou que dentre os metais investigados, Cd, Pb, Cu, Cr e Ni, o Cr e o Ni foram os que apresentaram maiores teores ao longo do período em estudo. Utilizando indicadores estatísticos de qualidade do sedimento, foi observado que Cr e Ni apresentaram valores que ultrapassaram o limite inferior TEL (valor guia canadense) indicando assim, um efeito deletério ocasional sobre a biota aquática do ambiente em estudo. Análises de componentes principais (PCA) utilizando como variáveis os parâmetros físico-químicos e as concentrações dos metais investigados, ressaltou a influência dos parâmetros STD e condutividade, M.O e pH no agrupamento dos dados e mostrou ainda que, as diferenças nos teores de metais entre os meses em estudo (período chuvoso e de seca) foram mais relevantes do que as diferenças entre os pontos de coleta investigados. A partir dos resultados e levando-se em conta os parâmetros medidos no trecho do rio, verificou-se que não há evidência de que o efluente têxtil até o presente momento, esteja afetando as características do Rio Piranhas.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / In the extraction and production of oil are generated many effluents and among them is produced water, water extracted along with oil, which distinguished by its large volume generated. There are present, among other contaminants, the trace metals. The Japaratuba river was used as a receiving body of waste generated in the fields of oil production from Carmópolis-SE, for many years and previous studies showed that the sediments are contaminated with copper, lead and zinc. The objective of this study was to reassess the environmental conditions of the Japaratuba river in the regions receiving the discharges from the fields of oil exploration after five years of removal of these evictions. Samples of surface sediments were collected along the river, at the same points in the previous study. We determined partial and total concentrations of Cu, Cd, Zn, Co, Al, Fe, Mn, Ba, V, Cr e Ni and in relation to the abundance of these we find: > Fe > Ba > Mn > Zn > Cr > Pb ~ Cu > Ni > Co > V > Cd. The lowest concentrations of metals were found at points P8 and P9 (near the mouth) and the highest concentrations for most metals analyzed were found at the point P3, one of the regions most affected the old dumps. Comparing the total concentrations in the study done previously observed that in the points P3, P5, P6, P7 and P8 the concentrations of all metals remained virtually unchanged or slightly increased, showing that the environment is not yet recoverd. As for the point P4 was noted an increase in concentration for all metals that can be explained by a possible remobilization of metals. Iron was chosen as standard elements to have shown better correlation than aluminum. The normalization of the results identified that the sediments altered by greater number of metals were related to the point P1, which were observed abnormal concentrations of Cu, Ba, Co, Ni, Pb and Al, followed by the point P5 contaminated by Cu, Cd, Co, Cr and Mg and point P6 changed by Co, Ni, Pb and Zn. Since the points P4, P7, P8 and P9 are not significantly contaminated by any of the metals analyzed, and the point P3 despite having the highest concentrations of metals are changed only by Cr. The lowest enhancement factor was found at the points P8 and P9 and the highest values for points P1, P3 and P4, the most affected by ancient discharges produced water, showing once again the non-recovery of the environment. The highest percentages of organic carbon and total nitrogen were found at the points P3, P4 and P5, were rightly places most affected by the effluent water produced. The values of the ratio of organic carbon and total nitrogen (Corg / Ntotal) for Japaratuba river sediments ranged from 17.29 to 21.63, except at the point P1 (444.50), whose value was much higher than that found in other points due to the low percentage of Ntotal this site. The values found are higher than the Redfield ratio (6,6:1) suggesting that the sediments studied the origin of organic matter is predominantly terrigenous and anthropogenic sources are more likely in this case the produced water discharges. / Na extração e produção do petróleo são gerados muitos efluentes e dentre eles encontra-se a água produzida, água extraída junto com o óleo, que se destaca pelo seu grande volume gerado. Nela estão presentes, dentre outros contaminantes, os metais traço. O rio Japaratuba era utilizado como corpo receptor desses efluentes gerados nos campos de produção de petróleo de Carmópolis-SE, durante muitos anos e estudos anteriores mostraram que os sedimentos estão contaminados por cobre, chumbo e zinco. O objetivo deste trabalho foi reavaliar as condições ambientais do rio Japaratuba, nas regiões que recebiam os descartes dos campos de exploração de petróleo após cinco anos de retirada destes despejos. As amostras dos sedimentos superficiais foram coletas ao longo do rio, nos mesmos pontos do estudo anterior. Foram determinadas concentrações parciais e totais dos metais Cu, Cd, Zn, Co, Al, Fe, Mn, Ba, V, Cr e Ni e em relação à abundância destes encontramos: Al > Fe > Ba > Mn > Zn > Cr > Pb ~ Cu > Ni > Co > V > Cd. As menores concentrações dos metais foram encontradas nos pontos P8 e P9 (próximos a foz) e as maiores concentrações para a maioria dos metais analisados, foram encontradas no ponto P3, uma das regiões mais afetadas pelos antigos despejos. Comparando as concentrações totais com o estudo feito anteriormente observou-se que nos pontos P3, P5, P6, P7 e P8 as concentrações de todos os metais permaneceram praticamente inalterada ou pouco aumentaram, mostrando que o ambiente ainda não está recuperado. Já para o ponto P4 notou-se um aumento de concentração para todos os metais que pode ser explicado por uma provável remobilização dos metais. O ferro foi escolhido como elemento normalizador por ter apresentado melhores correlações que o alumínio. A normalização dos resultados permitiu identificar que os sedimentos alterados por maior número de metais foram os relacionados ao ponto P1, no qual foram observadas concentrações anormais de Cu, Ba, Co, Ni, Pb e Al; seguido dos ponto P5 contaminado por Cu, Cd, Co, Cr e Mn e P6 alterado por Co, Ni, Pb e Zn. Já os pontos P4, P7, P8 e P9 não estão contaminados significativamente por nenhum dos metais analisados e o ponto P3 apesar de possuir as maiores concentrações dos metais está alterado apenas pelo Cr. Os menores valores de fator de enriquecimento foram encontrados nos pontos P8 e P9 e os maiores valores foram para os pontos P1, P3 e P4, os mais atingidos pelos antigos despejos de água produzida, evidenciando mais uma vez a não recuperação do ambiente. Os maiores valores percentuais de carbono orgânico e nitrogênio total foram encontrados nos pontos P3, P4 e P5, lugares onde justamente eram mais afetados pelos efluentes de água produzida. Os valores da razão entre carbono orgânico e nitrogênio total (Corg/Ntotal) para os sedimentos do rio Japaratuba variaram entre 17,29 a 21,63, exceto no ponto P1 (444,50), cujo valor foi muito superior ao encontrado nos outros pontos devido ao baixo percentual de Ntotal neste local. Os valores encontrados são superiores a relação de Redfield (6,6:1) o que sugere que nos sedimentos estudados a origem da matéria orgânica é predominantemente terrígena e fontes antrópicas são as mais prováveis, neste caso os despejos de água produzida.

No Cearà a zona costeira representa apenas 14,38% do territÃrio estadual, mas possui 48,9% da populaÃÃo do estado (IBGE, 2002. Na RegiÃo Metropolitana de Fortaleza (RMF) a densidade demogrÃfica da Zona Costeira Cearense (ZCC) aumenta para 598,00 hab/km2, atingindo valores ainda maiores quando focada a cidade de Fortaleza (6.814 hab/km2). Na dÃcada de 70, Fortaleza teve um salto de crescimento urbano, desordenado, na sua Ãrea costeira, com uma sÃria de construÃÃes que afetaram de maneira direta a sua linha de costa, tais como o antigo e atual porto de Fortaleza. Assim, este estudo teve por objetivo avaliar a influÃncia das atividades antrÃpicas sobre a emissÃo de metais e sobre a distribuiÃÃo e partiÃÃo geoquÃmica destes metais contidos nos sedimentos da regiÃo costeira da RMF. Analisados os teores de Hg, Cu, Cd, Pb, Zn, Al e Fe, nos sedimentos costeiros coletados em duas campanhas, nos perÃodos de chuva e seca, nÃo foi encontrada diferenÃa estatÃstica entre resultados obtidos relativos Ãs diferentes campanhas, exceto para o Fe. Os teores mÃdios obtidos foram: 0,72 a 17,54 ng.g-1 de Hg, 0,32 a 4,64 μg.g-1 de Cu, 0,13 a 0,77 μg.g-1 de Cd, 3,29 a 13,00 μg.g-1 de Pb, 1,81 a 18,64 μg.g-1 de Zn, 0,78 a 9,12 mg.g-1 de Al, 0,76 a 9,27 mg.g-1 (PerÃodo chuvoso) e 1,28 a 13,92 mg.g-1 (PerÃodo de seca) de Fe. Todos os metais apresentaram correlaÃÃes significativas com os principais carreadores geoquÃmicos, isto à com a matÃria orgÃnica, o alumÃnio e o ferro, menos com os carbonatos, mostrando que este substrato nÃo à um retentor geoquÃmico eficaz de metais. Apesar do oceano ser um bom diluidor de contaminantes foi verificado Ãreas de concentraÃÃes de metais prÃximas à linha de costa, à regiÃo do porto e à saÃda do EmissÃrio Submarino de Fortaleza (ESF) se dispersando no sentido E-W da deriva litorÃnea. O ESF mostrou-se ser fonte pontual de mercÃrio, cobre, zinco, cÃdmio e chumbo, entretanto o enriquecimento do sedimento por Hg, Cu e Zn ainda à de baixo grau. TambÃm foi observado que o runoff urbano à importante emissor de Cd e Pb, tendo em vista as elevadas concentraÃÃes encontradas prÃximas à linha de costa. A distribuiÃÃo dos metais mostrou que hà dois importantes fatores determinantes do comportamento destes metais em sedimentos costeiros da RMF. O primeiro fator està relacionado aos carreadores geoquÃmicos que predominantemente influenciam o comportamento do cobre, do chumbo e do zinco. O segundo fator està relacionado à proximidade e/ou intensidade das Ãreas fontes e dominou o comportamento do Hg e do Cd. / The coastal zone of Cearà State corresponds to only 14.38% of the Stateâs territory but harbors about 48.9% of its total population. The Metropolitan Region of Fortaleza (RMF), the Stateâs Capital population density at the coastal zone reaches 598 inhab/km2, and 6.814 inhab/km2 when only the city of Fortaleza itself is considered. During the 1970âs, Fortaleza witnessed an accelerated and unplanned urban growth along its coastal zone including engineering works, which affected the coastline itself, including the Fortaleza Harbor and may have increased pollutants emissions to the coastal region. Therefore, this study aims to evaluate the influence of these antropogenic developments on the emissions of trace metals and their distribution and geochemical partitioning in bottom sediments collected along the RMF coastal region. In two field campaigns, in the rain and dry season, the concentrations of Hg, Cu, Cd, Pb, Zn, Fe and Al, were measured in bottom sediments of the coastal zone. There was no significant difference between the two campaigns for all trace metals, except for Fe. Measured concentrations varied between 0.72 to 17.54 ng.g-1 for Hg; 0.32 to 4.64 μg.g-1 for Cu; 0.13 to 0.77 μg.g-1 for Cd; 3.29 to 13.00 μg.g-1 for Pb; 1.81 to 18.64 μg.g-1 for Zn; 0.78 to 9.12 mg.g-1 for Al, 0.76 to 9.27 mg.g-1 (rain season) and 1.28 to 13.92 mg.g-1 (dry season) for Fe. All trace metals concentrations presented significant positive correlation with the major geochemical carries analyzed, i.e. organic matter content, Aluminum and Iron, except for carbonates, carbonates are not efficient carriers of metals in these metals. Although the oceanic water mass acts as a large diluter of contaminants, areas of higher trace metal concentrations were observed close to the shoreline, at the area of influence of the Fortaleza Harbor and near the outlet of a submarine wastewater outfall. Concentrations decrease in an E-W direction following the littoral drift. The submarine wastewater outfall of Fortaleza showed an important point source of Hg, Cu, Zn, Cd and Pb. Although absolute concentrations of these trace metals were, in general, low. The higher concentrations along the shoreline suggest that urban runoff is also a significant source of trace metals, in particular of Cd and Pb. The spatial distribution of trace metals concentrations showed two important factors determining the behavior of trace metals in the bottom sediments of the RMF. The first factor is related to the concentrations of the geochemical carriers, which influence the behavior of Cu, Pb and Zn. The second factor is the proximity and/or the intensity of area sources and dominated the behavior of Hg and Cd.

O processamento anaeróbio da vinhaça se apresenta como uma alternativa para a recuperação de energia (biogás), e reaproveitamento das suas características nutricionais através da disposição no solo. Com o intuito de elevar a eficiência energética, o presente trabalho teve como objetivo estimular a produção de metano em reatores anaeróbios em batelada de lodo granular adaptado, alimentados com vinhaça de usina sucroalcooleira, por meio da adição de metais traço. Foram avaliadas as suplementações da vinhaça com Co, Zn, Mo, Ni, Mn e W. Na Fase 1 foram realizados 4 ensaios, os reatores foram analisados individualmente nas concentrações 200 μg.L-1, 350 μg.L-1, 500 μg.L-1 e 800 μg.L-1. Na Fase 2 verificou-se o comportamento dos metais em conjunto, à concentração de 350 μg.L-1 de cada micronutriente (Co, Ni, Zn, Mo, Cu e Mn). Os dados de produção acumulada de CH4 foram ajustados pelo modelo modificado de Gompertz, e foram obtidas as constantes cinéticas. Na Fase 1, verificou-se que a concentração de 200 μg.L-1 de Co foi a mais adequada aos experimentos e apresentou a maior velocidade máxima de produção de CH4, 121,30 mL.d-1 (aumento de 17% na taxa de produção de metano). Nesta mesma Fase, o W apresentou indícios de inibição à concentração de 800 μg.L-1, e os demais metais exibiram os melhores resultados nesta mesma concentração, a velocidade de produção (Rm) aumentou para o Mn (26%), Ni (25%), Cu (21%) e Mo (19%), e os rendimentos mais expressivos foram para Mo (0,267 mL CH4.mg-1 DQOrem), Zn (0,240 mL CH4.mg-1 DQOrem) e Ni (0,232 mL CH4.mg-1 DQOrem). A Fase 2 não apresentou resultados satisfatórios, as verificações não indicaram variação relevante entre os reatores do ensaio e controle. / Anaerobic processing of vinasse is presented as an alternative to energy recovery (biogas), and reuse of its nutritional characteristics through the provision on the ground. In order to increase energy efficiency, this study aimed to stimulate methane production in adapted anaerobic batch reactors with granular sludge fed with vinasse from sugarcane biorefineries, through the addition of trace metals. The supplementation vinasse were evaluated with Co, Zn, Mo, Ni, Mn and W. In phase 1 four essays were realized, and micronutrient were analyzed individually in concentrations of 200 μg.L-1, 350 μg.L-1, 500 μg.L-1 and 800 μ.L-1. In phase 2 it was observed the behavior of metal together, with micronutrients concentration of 350 μg.L-1 (Co, Ni, Zn, Mo, Cu e Mn). The data of methanes production were adjusted by Gompertz modified model and kinetics constants were obtained. In phase 1 it was verified that the concentration of 200 μg.L-1 of Co was optimal for the experiments and showed the highest maximum production velocity of CH4, 121,30 mL.d-1 (increase of 17%). In this phase W showed evidence of inhibition at a concentration of 800 μg.L-1, and other metals showed the best results in the same concentration. The velocity of production (Rm) increased to Mn (26%), Ni (25%), Cu (21%) e Mo (19%), and the most significant yields were to Mo (0,267 mL CH4.mg-1 DQOrem), Zn (0,240 mL CH4.mg-1 DQOrem) and Ni (0,232 mL CH4.mg-1 DQOrem). Phase 2 did not show satisfactory results.

Made available in DSpace on 2016-08-19T12:56:48Z (GMT). No. of bitstreams: 1 DISSERTACAO ALESSIO COSTA ROBSON.pdf: 887348 bytes, checksum: 0ec76a84f20ac6f686829b12c314fc0c (MD5) Previous issue date: 2014-07-30 / The geochemical fractions of Cd, Pb, Cu, Cr, Ni, Zn were determined according to the protocol developed by the Comunnity Bureau of Reference (BCR). The fractions of the protocol are divided into exchangeable (F1), reducible (F2), oxidisable (F3). A new fraction, the residual (F4), was included in the fractionation. The concentration of metals was determined by atomic emission spectrometry by inductively coupled plasma (ICP-OES). In addition, a mobility experiment was conducted by spiking a standard solution of metals to soils and subsequent application of the BCR protocol. The results of fractionation in the original soils detected only the presence of Pb, distributed in exchangeable (F1) and residual fractions (F4), indicating that soils are not contaminated. The mobility experiment showed that added metals in soils were retained in the fractions F1 and F3. Most acid soils have lower metal immobilization metals in fraction F1 (r2 = 0.99). The decreasing order of metals in each fraction contaminated soils was: F1 (55.3%)> F3 (18.75%)> F2 (6.35%). The application of principal component analysis (PCA) identified that the Cr showed higher affinity to organic fraction (F3), followed by Cu. The soils of the industrial district do not have values that offer risk to the ecosystem. In turn, these soils, due to its acidity and low organic matter content, provide unfavorable conditions to metal retention, favoring leaching in case of eventual contamination. / As frações geoquímicas dos metais Cd, Pb, Cu, Cr, Ni, Zn foram determinadas conforme o protocolo desenvolvido pelo Comunnity Bureau of Reference (BCR). As frações do protocolo são divididas em trocável (F1), redutível (F2), oxidável (F3). Uma nova fração, a residual, foi incluída no fracionamento. A concentração de metais foi determinada por espectrometria de emissão atômica por plasma indutivamente acoplado (ICP-OES). Adicionalmente, foi conduzido um experimento de mobilidade mediante adição de uma solução-padrão de metais aos solos e posterior aplicação do protocolo BCR. Os resultados do fracionamento nos solos originais apresentaram detectaram apenas a presença de Pb, distribuídos em frações trocáveis(F1) e residuais, indicando que os solos não estão contaminados. O experimento de mobilidade demonstrou que os metais adicionados nos solos ficaram retidos nas frações F1 e F3. Os solos mais ácidos apresentam menor imobilização de metais na fração F1 (r2 = 0,99). A ordem decrescente dos metais em cada fração dos solos contaminados foi: F1 (55,3%) > F3 (18,75%) > F2 (6,35%). A aplicação da análise do componente principlal (PCA) permitiu identificar que o Cr apresentou maior afinidadepela fração orgânica (F3), seguido pelo Cu. Os solos do distrito industrial investigado não apresentam valores que oferecem risco ao ecossistema. Por sua vez, esses solos, devido a sua acidez e baixo teor de matéria orgânica, propriciam condições desfavoráveis a retenção de metais,favorecendo a lixiviação dos mesmos em caso de eventual contamainação. .

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2016-04-11T16:45:54Z No. of bitstreams: 1 Dissertação Christiane Monte.pdf: 2209030 bytes, checksum: eeebb11c7f77055af279832c47fc6546 (MD5) / Made available in DSpace on 2016-04-11T16:45:54Z (GMT). No. of bitstreams: 1 Dissertação Christiane Monte.pdf: 2209030 bytes, checksum: eeebb11c7f77055af279832c47fc6546 (MD5) / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências-Geoquímica. Niterói, RJ / A ressuspensão de sedimentos por processos naturais ou atividades antrópicas (como as dragagens) pode afetar a biodisponibilidade de metais-traço. Esta hipótese foi testada numa área da Baía de Sepetiba (RJ) afetada por elevada contaminação por Cd e Zn, que recebe aporte fluvial de efluentes industriais e urbanos. Desta forma, o objetivo geral do presente estudo foi avaliar os efeitos da ressuspensão de sedimentos da região afetada pelo Saco do Engenho (Baía de Sepetiba) sobre a biodisponibilidade de metais-traço potencialmente tóxicos (Cd, Cu, Ni, Pb e Zn), por meio de ensaio laboratoriais, como estratégia de abordagem visando subsidiar a avaliação de risco ambiental associado à dragagem. Amostras de 12 pontos de amostragem foram coletadas próximas ao Canal do Saco do Engenho e do Porto de Itaguaí e submetidas a dois intervalos de tempo de ressuspensão (1 hora e 24 horas). Com a exceção do Ni, os metais-traço superaram os valores de background locais. Em particular, concentrações muito elevadas de Cd e Zn foram observadas, acima dos valores de background locais 5-71 vezes e 2-56 vezes, respectivamente, e até 16 e 27 vezes acima dos valores orientadores de qualidade de sedimentos de Nível 1 adotados pela Resolução CONAMA 454/2012, respectivamente. Houve predominância da fração fracamente ligada (extraída em HCl 1 mol/L), exceto para o Ni, ocorrendo tendência de redução da biodisponibilidade potencial com a distância do Canal do Saco do Engenho em relação a Cd, Cu, Pb e Zn. As mudanças nas concentrações fracamente ligadas de Cd e Zn após a ressuspensão foram acima dos valores orientadores de Nível 1 em apenas duas amostras. Foi evidenciado que compostos de Fe e Mn são importantes fatores de influencia sobre a fração fracamente ligada aos sedimentos, enquanto o carbono orgânico total (COT) mostrou correlação com Cd, Zn e Cu na fração fortemente ligada aos sedimentos (extraída em HNO3 concentrado), demonstrando a importância da matéria orgânica para a preservação destes metais nesta fração menos susceptível a incorporação biológica. Embora tenham sido encontradas concentrações de sulfetos voláteis em meio ácido (AVS) suficientes para reter os metais simultaneamente extraídos (SEM) na fase sólida na maior parte das amostras, as concentrações de AVS não apresentaram nenhuma correlação com os metais. Os resultados evidenciam que a ressuspensão afeta a biodisponibilidade de diferentes metais, principalmente no primeiro intervalo de tempo (1 hora), refletindo mudanças abruptas em função da exposição a condições oxidantes / The re-suspension of sediments due to natural processes or anthropogenic activities (such as dredging) can influence the trace metal bioavailability. This hypothesis was tested in an area of Sepetiba Bay (RJ) affected by elevated contamination by Cd and Zn, which receive industrial and urban effluents by fluvial input. Therefore, the main objective of this study was to evaluate the effects of re-suspension of sediments from the region affected by Saco do Engenho (Baía de Sepetiba) on the bioavailability of potentially-toxic trace metals (Cd, Cu, Ni, Pb and Zn), by performing laboratory assays, as a strategy to subside the environmental risks associated to dredging. Samples from 12 sampling points were collected near the Saco do Engenho creek and the Itaguaí Harbor, being submitted to two re-suspension time intervals (1 hour and 24 hours). With the exception of Ni, trace metals exceeded local background values. In particular, very high concentrations were found for Cd (5‒71 times local background) and Zn (2‒56 times local background), corresponding to values above sediment quality guideline of Level 1 adopted by the CONAMA resolution 454/2012 (up to 16-times higher for Cd and 27-times higher for Zn). There was predominance of weakly-bound fraction (extracted in 1 mol/L HCl), except for Ni, occurring a tendency of decrease in the potential bioavailability with the distance from the Saco do Engenho creek in relation to Cd, Cu, Pb and Zn. Changes in the weakly-bound concentrations of Cd and Zn after re-suspension were above the Level 1 for two samples only. It was evidenced that Fe and Mn compounds are important factors affecting the weakly-bound fraction, while total organic carbon (TOC) showed correlations with Cd, Zn and Cu strongly-bound fraction (extracted in concentrated HNO3), demonstrating the importance of organic matter for the preservation of these metals in such fraction less susceptible to biological incorporation. Although there were acid-volatile sulfide (AVS) concentrations sufficient to retain simultaneously-extracted metals (SEM) in the solid phase in most samples, the AVS concentrations were not correlated with metals. Results evidence that re-suspension affects the bioavailability of different metals, principally in the first time interval (1 hour), reflecting abrupt changes due to exposure to oxidizing conditions

Les estuaires sont des systèmes hautement dynamiques où interagissent des processus biogéochimiques complexes qui influent sur le devenir de la matière organique et non organique. La confrontation des eaux fluviales et marines induit des changements rapides des principaux facteurs structurant la distribution des organismes vivants et gouvernant la spéciation de certains éléments traces entre phase particulaire et dissoute, ex : gradient de salinité, teneurs en matières en suspension (MES). Ce travail vise à étudier l’estuaire de la Charente, principal fleuve influançant le bassin de Marennes-Oléron (première zone ostreicole française) afin (i) de caractériser la structure de la communauté zooplanctonique en relation avec les paramètres environnementaux, (ii) le fonctionnement de la base du réseau trophique de l’estuaire (identification des sources de matière organique exploitée par les organismes zooplanctoniques et suprabenthiques) et (iii) d’établir un état de contamination par les métaux des compartiments biotiques. L’estuaire de la Charente se distingue par des concentrations en MES extrêmement élevées, présentant néanmoins une contribution importante de la matière organique (efflorescence phytoplanctonique printanière en zone mésohaline et production microphytobenthique). La zone de turbidité maximale semble correspondre à un écotone qui contrôle les flux de matière organique et la distribution des organismes. Le mélange physique des particules issues des systèmes dulcicoles et marins adjacents à l’estuaire avec cette forte charge de matériel resuspendu conduit à une homogénéisation des signatures isotopiques et métalliques particulaires en été et automne le long du gradient de salinité. Les quatre assemblages zooplanctoniques identifiés sont structurés spatialement par la salinité et la concentration en MES et temporellement par les variations de température et de débit fluvial. Malgré la dominance quantitative du matériel détritique au sein du pool de matière organique particulaire (MOP), il semble que les 5 taxons planctoniques ou suprabenthiques dominants étudiés (Eurytemora affinis, Acartia spp., Daphnia spp., Neomysis integer, Mesopodopsis slabberi) présentent une sélectivité importante vis-à-vis de sources primaires distinctes. Cette succession spatio-temporelle d’espèces sélectives conduit à une multiplication des flux trophiques et semble ainsi optimiser à l’échelle annuelle l’exploitation de la MOP disponible. Les concentrations en Cd, Cu, Hg, Pb, V et Zn ont par ailleurs été mesurées dans près de 40 taxons estuariens (zooplancton, benthos, poissons). Malgré des concentrations en métaux dissous et particulaires plus faibles que dans les grands estuaires européens subissant une pression anthropique importante (Seine, Gironde), les niveaux de contamination mesurés dans les différents compartiments biotiques semblent globalement équivalents. Les évènements brefs (crue hivernale, efflorescence phytoplanctonique printanière) altèrent toutefois fortement ce schéma général en modifiant les sources primaires de matière organique disponibles et les concentrations métalliques particulaires (Cd notamment). / Estuaries are highly dynamic systems where complex biogeochemical greatly affect the fate of organic and non-organic matter. The physical mixing of freshwater and saltwater leads to high variability in the main drivers controlling organisms distribution and trace metals partitioning between the particulate and dissolved phases: eg. salinity gradient, suspended particulate matter concentration (SPM). This work aims thus at studying the Charente estuary, which is the main river discharging into the Marennes-Oléron Bay (first oyster producing area in France) in order to (i) characterize the zooplankton community structure and relate it to the main environmental parameters, (ii) identify the main organic matter sources contributing to the functioning of the planktonic food web and (iii) to characterize contamination of the biological compartment of this estuary. Although being one of the most turbid estuaries in Europe, the Charente estuary displays quite high organic matter contribution, especially through a spring phytoplankton bloom in the mesohaline area and microphytobenthic production. The maximum turbidity zone (MTZ) displays some ecotonal characteristics, controlling both organic matter fluxes and organisms distribution. The physical mixing of terrestrially and marine derived particles within the high load of resuspended estuarine particles leads to quite homogeneous isotopic and metallic signatures in particles all along the salinity gradient during summer and autumn. Salinity and SPM concentration significantly controls the spatial distribution of the four zooplankton assemblages identified while temperature and river discharge controls their temporal variations. Despite the quantitative dominance of terrestrially derived detrital organic matter, the five dominant planktonic and suprabenthic taxa studied (Eurytemora affinis, Acartia spp., Daphnia spp., Neomysis integer, Mesopodopsis slabberi) display strong selectivity toward different organic matter sources. At the annual scale, the exploitation of the available stock of organic matter seems optimized by this spatio-temporal succession of selective species that leads to multiple trophic pathways. In addition, the concentrations of Cd, Cu, Hg, Pb, V and Zn were measured in nearly 40 estuarine taxa (zooplankton, benthos, fishes). Although particulate and dissolved metal concentrations were somewhat low as compared to those measured in highly impacted European estuaries (Seine, Gironde), the contamination levels recorded in these biotic compartments were of the same order of magnitude. Moreover, brief events such as high water levels and phytoplankton blooms greatly affect this overall pattern by modifying the available organic matter sources and particulate trace metals concentrations (especially Cd).

Aucune étude physicochimique majeure des eaux du fleuve Chari n’a été réalisée malgré le fait que depuis l’indépendance du Tchad (1960), quelques usines agroalimentaires, des hôpitaux, des usines textiles, des abattoirs… se soient installés sur ses rives. Les résultats des analyses obtenus après un suivi de 2008 à 2010 ont montré la présence des métaux traces dans le Chari. Sur l’ensemble des échantillonnages d’eau analysés, le fer est l’élément métallique majeur devant le manganèse, le zinc et le nickel. Ces résultats varient en fonction des périodes de prélèvement (saison des pluies ou saison sèche). La plupart des valeurs obtenues dépassent largement les seuils acceptables selon les recommandations de l’OMS. La présence des métaux traces dans le Chari résulte aussi bien du processus naturel que de l’activité humaine. Bien que les concentrations de Ni, Cr, Co, Mn et Zn ne soient pas aussi élevées que celle du fer, le profil de répartition de ces éléments entre les différents sites montre une certaine similarité. Les valeurs moyennes de pH indiquent que les effluents ont un caractère légèrement alcalin, tandis que celles relatives à l’oxygène dissous sont satisfaisantes. De ce fait, les eaux du Chari sont impropres, du point de vue physicochimique voire potentiellement dangereuse pour la santé environnementale et humaine. La lutte contre les pollutions doit être entreprise le plus précocement possible / No physicochemical major study of water of the Chari river was carried out in spite of the fact that since the independence of Chad (1960), some food agro factories, hospitals, textile factories, slaughter-houses… were installed on its banks. Also, this work aims to the “contribution to the analytical study of the pollutants (particularly heavy metals) in waters of the Chari river crossing the town of N’Djamena” using the suitable chemical techniques. The results of the analyses obtains after a follow-up from 2008 to 2010 showed the presence of trace metals in the Chari river. On the whole of analyzed water samplings, iron is the major metal element in front of manganese, zinc and nickel. These results vary according to the periods of taking away( rainy season or dry season). The majority of the values obtained largely exceed the acceptable thresholds according to recommendations of WHO. The presence of trace metals in the Chari river results as well from the natural process as of human activity. Although the concentrations of Ni, Cr, Co, Mn, Cu and Zn are not as high as those of iron, the profile of distribution of these elements between the various sites shows a certain similarity. The average values of pH indicate that the effluents are slightly alkaline, while those relating to dissolved oxygen are satisfactory. So the waters of Chari are unsuitable, from the physicochemical point of view, even potentially dangerous for environmental and human health. The control of pollution must be undertaken the most preciously as possible

Les travaux de cette thèse sont consacrés principalement à l'optimisation d'une méthode de remédiation électrocinétique (EK) comme une technologie appropriée pour le traitement de sédiments de dragage de faible perméabilité hydraulique et multi-contaminés (en éléments traces (ET), hydrocarbures aromatiques polycycliques (HAP) et polychlorobiphényles (PCB)). Cette étude porte également sur l’effet du traitement EK sur l’évolution de la toxicité des sédiments. Après une revue bibliographique, une seconde partie a été dédiée aux méthodes d’analyse des contaminants, avec un focus sur leur extraction de la matrice sédimentaire ; ainsi, une nouvelle méthode d’extraction par dispersion de la matrice solide (MSPD) a été développée, pour une extraction rapide et simultanée des HAP et de PCB et une purification de l’échantillon, qui s’est avérée plus efficace que la méthode d’extraction assistée par micro-ondes (MAE). Plusieurs études expérimentales (à différentes échelles) de remédiation électrocinétique ont été décrites dans une troisième partie ; ces études ont été menées sur un sédiment reconstitué ou des sédiments de dragage portuaire. De nombreuses combinaisons de tensioactifs et d’agents chélatants ont été testées comme agents d’amélioration pour abaisser simultanément la concentration en métaux (Cd, Cr, Cu, Pb, Zn) et des HAP/PCB. Le choix a été effectué en raison notamment de leur faible toxicité potentielle, en vue de pouvoir les appliquer ultérieurement pour une restauration sur site : (bio)surfactants (Rhamnolipides, Saponine et Tween 20) combinés avec des agents chélatants (acide citrique (CA) et EDDS). Les résultats obtenus montrent que les métaux (à l'exception de Cr) sont difficiles à extraire de ces sédiments de dragage portuaire à caractère réducteur, qui présentent une capacité tampon élevée, une perméabilité hydraulique très faible et une teneur en matière organique élevée. En revanche, les HAP et les PCB fournissent de meilleurs taux d'abattement (29,2% et 50,2%, respectivement). Dans une quatrième partie, l'efficacité du procédé EK a également été évaluée à travers l’évolution de la toxicité aiguë des sédiments traités sur les copépodes E. affinis exposés aux élutriats de sédiments. Les résultats ont montré que l'utilisation de CA,des biosurfactants et du Tween 20 n'a pas eu d'impact significatif sur la toxicité des sédiments traités. Cependant, les copépodes E. affinis étaient sensibles aux faibles valeurs de pH et aux conditions très oxydantes, ainsi qu’à la présence de Cu et, dans une moindre mesure, de Pb, à condition toutefois qu’ils soient rendus plus mobiles et biodisponibles. En revanche, la toxicité a été peu et même négativement corrélée aux concentrations des HAP et des PCB après le traitement EK, probablement en raison de la production de métabolites oxydés des HAP et des PCB, plus toxiques que les composés natifs. / This thesis research is mainly devoted to the optimization of an electrokinetic (EK) remediation process as a promising technology for treating multi-contaminated (trace metals, polycyclic aromatic hydrocarbons (PAHs) and polychlorobiphenyles (PCBs)) dredged harbor sediments of low permeability. This study is also investigating the effect of the EK treatment on the evolution of sediment toxicity. After a bibliographic review, asecond part of this study was dedicated to the analytical methods carried out for the characterization of the sediment and its contaminants, particularly to their extraction from the sediment matrix; thus a new extraction method, through matrix solid phase dispersion (MSPD) was developed, for a fast and simultaneous extraction of both PAHs and PCBs, and a sample purification.MSPD appeared more efficient than the microwave assisted extraction (MAE) method. Thereafter many EK experiments (at different scales) were described in a third part. EK remediation tests were performed using a spiked model sediment or natural harbor dredged sediments. Many combinations of surfactants and chelators were tested as EK enhancing agents for decreasing simultaneously metal (Cd, Cr, Cu, Pb, Zn) and PAH/PCB levels. Their choice was done because of their possible low toxicity with a view to use them for future site restoration: (bio)surfactants (rhamnolipids, saponin and Tween 20) combined with chelators (citric acid (CA) and EDDS). The results showed that metals (except Cr) were difficult to remove from this kind of dredged sediment owing to its reductive character, to its high buffering capacity, to its very low hydraulic permeability and to its high organic matter content. However PAHs and PCBs showed better removal levels (29.2% and 50.2%, respectively). In a fourth part, the efficiency of the EK process was also assessed by measuring the evolution of the acute toxicity of the treated sediment on E. affinis copepods exposed to sediment elutriates. The results showed that using CA, biosurfactants or Tween 20 as enhancing agents did not significantly impact the toxicity of the treated sediment. However, E. affinis copepods were significantly sensitive to low pH values and oxidative conditions, to Cu, and to a lesser extent to Pb amounts, if they were transformed in more mobile and bioavailable forms. In contrast, acute toxicity was only slightly and even negatively correlated to PAH and PCB amounts after EK treatment, probably due to the production of oxidized metabolites of PAHs and PCBs, more toxic than the parent compounds.