Os recursos hídricos urbanos são de grande importância para os municípios que têm desenvolvimento econômico crescente e aumento demográfico, sendo que a manutenção da qualidade da água dos mananciais de abastecimento para a população é imprescindível para a saúde e para diminuir o custo econômico. A bacia do Alto Jacaré-Guaçu, em cuja área está inserido o município de São Carlos/SP, tem como principais sub bacias a do Rio do Monjolinho e a do Ribeirão do Feijão, sendo este a principal fonte de abastecimento de água para a cidade. O trabalho foi proposto para avaliar a qualidade da água dos recursos hídricos da bacia do Alto Jacaré-Guaçu, através da análise das características limnológicas, das substâncias tóxicas e da comunidade de macroinvertebrados que permitem a indicação da qualidade da água. Foram efetuadas duas campanhas de amostragem em 1999: a) no período chuvoso (em março) e b) no período de estiagem (em agosto). Em março foram realizadas amostragens em 8 pontos e, em agosto, foram acrescidos mais 6 pontos, totalizando 14. Paralelamente, com o intuito de visualizar espacialmente os resultados e desta forma identificar as áreas com maior ou menor grau de impacto, foi elaborado um mapa com as sub-bacias correspondentes às áreas cuja água drena para cada um dos pontos de coleta. Os resultados obtidos demonstram que a qualidade da água no período da estiagem se torna mais critica devido à diminuição do fluxo da água. Com relação à poluição orgânica, a sub bacia do Monjolinho pode ser classificada em 3 grupos: a) trecho sem influência urbana, portanto não poluída ou ligeiramente poluída; b) trecho com influência da área urbana da cidade de São Carlos, sendo assim, fortemente poluída e c) trecho final do Rio Monjolinho, com uma poluição moderada ou em processo de recuperação. Quanto à presença de substâncias tóxicas analisadas as concentrações dos metais, em geral, apresentaram-se dentro dos limites da Resolução CONAMA 20/86, exceto o cobre, ferro, manganês e zinco. Já para os organoclorados, a maior parte da área da bacia não atende a Resolução Brasileira, detectando-se concentrações acima dos limites permitidos. Quanto à identificação dos diferentes impactos no uso da terra e da água na bacia do Alto Jacaré-Guaçu, pode-se citar, entre as atividades antrópicas que vem acelerando o processo de degradação ambiental, principalmente a qualidade da água :1- Falta de tratamento do esgoto doméstico, principalmente na área urbana; 2- Desmatamento contínuo levando a substituição da vegetação natural por monoculturas e pastagens; 3- Uso irregular do solo, causando erosão e assoreamento nos corpos de água; 4- Expansão sem controle da área urbana próximo às margens e principalmente nas nascentes dos corpos de água e 5-Falta de controle na comercialização e uso de defensivos agrícolas. / The water resources in urban areas are important for the municipalities in stage of economical development and demographic increase. The maintenance of quality of the water sources is indispensable for the human health and to reduce the economic costs. The Alto Jacaré-Guaçu basin, situated in São Carlos municipality, has as a principal sub-basins the Monjolinho River and Ribeirão do Feijão basins. Both are the main souce of water supply for the city. This study was proposed to analyze the water quality of the Alto Jacaré-Guaçu basin, according to the limnological conditions, toxic substances and utilization of macroinvertebrates as indicative of the water quality. Sampling was carried out in two periods: a) in the rainy season (March 1999) and b) in the dry season (August 1999). In March 8 stations were sampled, while in August 6 more stations were sampled, totalizing 14 stations. In Parallel, a map was elaborated with the sub-basins corresponding to the drainage area for each station in order to show spatially the results and to identify the areas with bigger or minor degree of impact. The results demonstrated that the water quality in the dry period became critical due to decreasing of the water flow. Concerning to the organic pollution, the sub-basin of Monjolinho can be classified under 3 groups: a) section without urban influence, with no or few pollution; b) section with no or few pollution; b) section with influence of the urban area of São Carlos city, being strongly contaminated and c) final section the Monjolinho River, with a moderate pollution or in process of recovery. In relation to the presence of toxic substances analyzed, the concentrations of metals generally appeared inside the limits of the Resolution CONAMA 20/86, except for copper, iron, manganese and zinc. For the organochlorine pesticides, the concentrations oberseved do not attend to the Brazilian Resolution, because the values were higler than the acceptable limits. Concerning to the identification of different impacts of the land and water uses in the Alto Jacaré-Guaçu basin, it is possible to identify the human activities that accelerate the process of environmental degration, specially for the water quality: 1- The lack of teatment of the domestic residues, specially in the urban area; 2- Continous deforestation and changing of natural vegetation to monocultures and pastures; 3-Irregular uses of the soil causing erosion and collapsing the water bodies; 4- Expansion without control of the urban area next to the margins and specially in the headwaters, and 5- Lack of control in the selling and uses of agricultural pesticides.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-10-04T15:44:46Z No. of bitstreams: 1 tese_renata_maria_completa.pdf: 1532064 bytes, checksum: db3c7a043c5eecc779b264a3e956dea2 (MD5) / Made available in DSpace on 2017-10-04T15:44:46Z (GMT). No. of bitstreams: 1 tese_renata_maria_completa.pdf: 1532064 bytes, checksum: db3c7a043c5eecc779b264a3e956dea2 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / Nos últimos anos observa-se um aumento crescente das atividades humanas, tanto científicas quanto turísticas, no ambiente antártico, sendo motivo de preocupação considerando-se que a Antártica é um ambiente de lenta recuperação. Ainda são escassos os estudos sobre o estabelecimento de relações entre a presença de contaminantes e seus efeitos na biota antártica. A contaminação pode ocorrer por processos antrópicos ou naturais e os efeitos destes impactos podem ser detectados e monitorados através da análise das alterações nas comunidades bentônicas. Estas comunidades podem ser consideradas boas indicadoras de impactos ambientais, já que possuem uma relação direta com a origem dos contaminantes acumulados nos sedimentos. Este trabalho avaliou os níveis de metais-traço encontrados no sedimento e em duas espécies circumpolares da megafauna bentônica antártica, a estrela-domar Odontaster validus e o molusco bivalve Laternula elliptica, com a finalidade de determinar se as mesmas podem ser utilizadas como indicadoras de impacto ambiental. Durante o verão austral de 2005/2006 foram realizadas coletas através de diferentes procedimentos, entre 15 e 40m de profundidade, em cinco estações dentro da Área Antártica Especialmente Gerenciada da Baía do Almirantado, Ilha Rei George: 1) Estação Antártica Comandante Ferraz; 2) Botany Point; 3) Punta Ullman; 4) Punta Plaza e 5) Refúgio II. Os seguintes metais foram quantificados tanto para o sedimento quanto para os organismos: Al, V, Cr, Mn, Fe, Ni, Cu, Cd, Ba, Pb e Zn. A concentração de metais variou entre os diferentes compartimentos corpóreos analisados. Para a espécie O. validus, as maiores concentrações de metais-traço (Mn, Ni, Cd, Ba, Pb) e do macronutriente Al, foram encontradas na parede do corpo. Cu, Cr, V e Zn apresentaram maior concentração no estômago, enquanto o macronutriente Fe concentrou-se preferencialmente nos cecos pilóricos. Para a espécie L. elliptica, as maiores concentrações de metais-traço (Mn, V, Ba, Cu) e dos macronutrientes Fe e Al, foram encontradas no sifão. Cd, Ni, Pb e Zn apresentaram maior concentração no rim enquanto o Cr foi mais concentrado no compartimento restos. A concentração de elementostraço nos compartimentos corpóreos de O. validus e L. elliptica não foi influenciada pelo tamanho do organismo (peso total do indivíduo). / Once the Antarctic environment has low recovery rates, the recent growth in the touristic and scientific activities is a serious issue for the scientific community. Few studies have tried to establish the links between the presence of contaminants and the antarctic biota. The contamination may be related to human or natural processes, and be monitored trough the benthic communities. These communities have a direct relation with the contaminants sources in the sediment. The present work analyzed the trace-metals levels found in the sediment and two circumpolar benthic megafauna species in Antarctica, the starfish Odontaster validus and the Antarctic clam Laternula elliptica. The objective was to establish if these species can be used as environmental indicators. Five stations was occupied during the austral summer of 2005/2006, between 15 and 40m deep, in the Antarctic Special Management Area of Admiralty Bay, George King Island: 1) Comandante Ferraz Antarctic Base; 2) Botany Point; 3) Punta Ullman; 4) Punta Plaza and 5) Refúgio II. Analyzes were conducted to quantify the presence of Al, V, Cr, Mn, Fe, Ni, Cu, Cd, Ba, Pb and Zn, both in the sediment and organisms. The metals concentrations vary in the different body compartments. Larger concentrations of (Mn, Ni, Cd, Ba, Pb) trace metals and Al macronutrient were found in the body walls of O. validus. Cu, Cr, V and Zn showed larger concentrations in the stomach and the Fe macronutrient in the caeca pyloric. For L. elliptica, larger trace metals (Mn, V, Ba, Cu) and macronutrients (Fe and Al) concentrations were found in the sifon, while Cd, Ni, Pb and Zn showed larger concentrations in the kidney. Cr presented larger concentrations in the remains compartment. The concentrations of trace elements in both O. validus and L. elliptica were not influenced by the body size (total individual weight).

L’objectif principal de ce travail de thèse est d’évaluer l'impact des activités anthropiques sur le fonctionnement des systèmes aquatiques. L’impact des rejets urbains de Fès sur le Sebou, l'une des plus grandes rivières du Maroc, a été choisi pour cette étude. Les eaux usées domestiques et industrielles de la ville de Fès (~1M hab), véhiculées par son affluent l’oued Fès, sont rejetées dans le Sebou quasiment sans traitement. Deux sites du Sebou, en amont et en aval des rejets de la ville de Fès, et un site situé sur l’oued Fès ont été étudiés. Une campagne de prélèvement de carottes de sédiments et onze campagnes mensuelles de prélèvement d’eau et de matières en suspension (MES) ont été effectuées dans le but de quantifier les apports en nutriments, éléments traces métalliques (ETM) et carbone organique afin d’étudier la dynamique de ces polluants. Les résultats obtenus ont mis en évidence une augmentation des concentrations de presque tous les éléments étudiés en aval de la ville de Fès aussi bien dans la colonne d’eau que dans les sédiments. L’étude des carottes sédimentaires a révélé une contamination modérée par les butylétains totaux (ΣBT) avec la prédominance du monobutyétain dans les trois sites d’étude et sur toutes les profondeurs. Les sédiments du Sebou, en amont de la ville de Fès se caractérisent par les teneurs les plus faibles en métaux alors que ceux de l’oued Fès présentent une forte pollution polymétallique, accentuée dans les sédiments de surface, ce qui reflète clairement la signature d'apports anthropiques récents résultant des rejets non traités de la ville de Fès. L’augmentation consécutive des teneurs des métaux dans les sédiments du Sebou en aval de la confluence Fès-Sebou traduit l'influence significative des particules polluées de l’oued Fès. Dans la colonne d’eau, les concentrations mesurées dans le Sebou en amont de la confluence Fès-Sebou sont proches des rivières naturelles, à l’exception de Cl-, Cr, Na+ et NO3- dont les concentrations traduisent des pollutions agricoles et/ou domestiques. En revanche, la signature anthropique des rejets de la ville de Fès apparait évidente dans les eaux de l’oued Fès qui montrent des concentrations très élevées en ETM dissous et particulaires. La majorité des ETM provenant des apports anthropiques subissent des changements importants de leur coefficient de distribution Kd et présentent un comportement non conservatif dans le mélange entre les eaux du Sebou et celles de l’oued Fès. Ces résultats ont été confirmés par le modèle WHAM qui permet de prédire correctement le fractionnement dissous/particulaire, du Cu, Pb et Zn. La spéciation chimique de ces éléments ainsi que leur répartition dissous/particulaire apparaissent significativement influencées par les conditions particulières (anoxie, forte contamination, teneurs importantes en matière organique) des eaux de l’oued Fès. Ces conditions sont aussi à l’origine du comportement non conservatif de la majorité des éléments lors d'un mélange Sebou/Fès, observé aussi bien dans la colonne d’eau que dans les sédiments. / The main goal of this PhD was to evaluate the impact of the anthropogenic activities (urban, industrial or agricultural activities) on aquatic systems. The Fez metropolitan area and its impacts on the Sebou River, the main Moroccan river, were chosen as a case study. The Fez agglomeration (~1M hab), is surrounded by the Fez River, receiving the wastewaters of this developing city and then flowing into the Sebou. This work was performed on two sites along the Sebou River (upstream and downstream from the confluence with Fez River), and one site in the Fez River, downstream from the Fez city. One sampling campaigns of sediment cores and eleven sampling campaigns were performed during low flow conditions to quantify nutrients, organic carbon and trace metals and to study the dynamic and the transport of trace elements in the Sebou and Fez rivers. The obtained results revealed a global increase of studied elements in the Sebou River from upstream to downstream sampling site, in both sediments and water column. A moderate level of contamination by butyltins was observed, with monobutyltin being the dominant species across all sites and depths. The lowest level of metal pollution was identified in the Sebou's sediments upstream Fez city. Whilst the Fez' sediments were heavily polluted and exhibited bottom-up accumulation trends, which clearly evidence recent inputs from the untreated wastewaters of Fez city. The increase of metal levels in Sebou downstream sediments reflects a significant contribution of polluted particles from the Fez River. Dissolved and particulate concentrations of most of the analyzed elements in the Sebou, upstream from Fez city, are close to the natural rivers, except Cl-, Cr, Na+ et NO3- probably due to untreated urban inputs from several small/medium-size towns located upstream Fez. In the opposite On the contrary, high dissolved and particulate trace metals concentrations in the Fez River clearly indicated strong anthropogenic inputs from Fez city. Most of the studied trace metals originated from anthropogenic sources, underwent significant changes of Kd and behaved non-conservatively in the Sebou/Fez waters mixing due to drastic changes of the waters quality (anoxic condition, high concentration, high organic matter content). Dissolved/particulate partitioning were correctly assessed by WHAM-VII modeling for Cu, Pb and Zn, depicting significant differences in chemical speciation in Fez River when compared to Sebou one.

L’étude du comportement des éléments métalliques est primordiale compte tenu leur effet souvent toxique dansde nombreux écosystèmes. Ces derniers lorsqu’ils interagissent avec la Matiere Organique (MO), peuvent formerdes complexes plus ou moins stables. Ainsi, la MO joue un rôle important dans leur spéciation chimique et leurtransport. Dans ce travail, l’analyse de cette complexation est réalisée par Quenching de Fluorescence (QF).Cette technique permet de modéliser la fixation des sites de complexation à l’aide d’une constante thermodynamiquedéterminée à partir d’un modèle 1 : 1. Le quenching de fluorescence a été mesuré par spectroscopie defluorescence en mode stationnaire et en mode résolue en temps. Les mesures de fluorescence en mode stationnairefournissent des Matrices d’Excitation et d’Émission de Fluorescence (MEEFs). L’extraction des différents composantsde ces MEEFs est effectué par séparation de sources : la décomposition multilinéaire CP/PARAFAC,qui permet de caractériser spectralement les composants. Les mesures par Spectroscopie Laser Résolue en Temps(SLRT) permettent une caractérisation spectrale et temporelle des composants fluorescents. L’étude des lois dedécroissance de la fluorescence induite par impulsion laser nanoseconde en l’occurrence a permis de déterminerle type d’interaction entre la MO et les quencheurs. Pour se faire, un algorithme de déconvolution temporellea été appliqué à chaque décroissance de fluorescence mesurée. L’interprétation des données temporelles a étéaccomplie en utilisant le graphique de Stern–Volmer. Les résultats des interactions du cuivre, de l’europiumet de l’uranium avec les Acides Humiques (AH) et les Acides Fulviques (AF) montrent des décroissances defluorescences importantes et des constantes de stabilité entre 2,04 et 4,52. Le cuivre a permis de valider notremodèle d’étude et l’interaction de l’europium et l’uranium avec les AH et AF étudiés a révélé des constantesde stabilité en général en bonne corrélation avec la littérature. Les résultats de la SLRT ont souvent révélé desdécroissances bi–exponentielles et des temps de vie entre 0,40 et 14 ns et montrent que les interactions étudiéesont principalement engendrer un quenching statique et donc la formation d’un complexe moléculaire à l’étatfondamental. Cette étude a donc permis par caractérisation spectrale et temporelle, de déterminer l’interactionde la matière organique avec les métaux plus ou moins toxiques. / The study of metal elements behavior, considering their impact in various ecosystems, is of paramount importance.The latter, upon contact with Organic Matter (OM) can form weak or strong stable complexes. Therefore,OM plays an important role in their chemical speciation and transport. The analysis of these properties is carriedout by Fluorescence Quenching (QF). This technique allows introspecting ligands–metal interactions andthe 1 : 1 modeling (one ligand site, one metal) gives information about the conditional thermodynamic constant.Fluorescence quenching was measured using steady–state and time–resolved fluorescence spectroscopy.The steady–state measurements provides Excitation and Emission Matrices of fluorescence (EEMs). The extractionof the different components from these matrices is carried out by a multi–mode factor analysis such asCP/PARAFAC, which allows a spectral composition of the samples. Time-Resolved Laser Spectroscopy (TRLS)measurements allow temporal and spectral characterization of the fluorescent components. Indeed, the study ofthe fluorescence decays induced by a nanosecond pulsed laser in this case allowed to measure the interaction betweenthe OM and the quencher. For those purposes, a fluorescence lifetime deconvolution algorithm was appliedto each fluorescence decay. Analysis of the fluorescence lifetime data was accomplished using the Stern–Volmerplot which gave reliable information on the quenching process that takes place. Copper, europium and uraniuminteractions with Humic Acids (HA) and Fulvic Acids (FA) shows significant fluorescence decays and stabilityconstants between 2.04 and 4.52. Copper allowed to calibrate our model study and the interactions of europiumand uranium with the HA and FA studied reported stability constants in agreement with the literature. TRLSresults have often revealed a bi–exponential decays and fluorescence lifetimes between 0.40 and 14 ns and showsthat the studied interactions mainly lead to static quenching and thus the formation of a molecular complex inthe ground state. This study has allowed spectral and temporal characterization to determine organic matterinteraction with toxic metals.

The Cretaceous Mowry Shale is an organic-rich, siliceous marine shale, and as such is a known source rock in the Western United States. Studies have documented that total organic carbon (TOC) in the Wind River Basin, Wyoming increases to the southeast. These studies cover large areas with limited sample sets. In this study, over 250 samples were collected near Lander, Wyoming to address spatial heterogeneity of TOC within the Mowry Shale at a much finer scale than previously examined. Samples were collected along five vertical sections at three localities, and following correlation of the vertical sections, which was strongly aided by the presence of regional bentonite horizons, samples were collected laterally from the same unit at regular 25-foot intervals. These samples were analyzed using pyrolysis and x-ray diffraction techniques. Average TOC values are fairly consistent within the study area (1.65%, with a range of 2.10% to 1.15%). Average Tmax values for vertical and lateral samples is 433 °C with a standard deviation of 7.25 °C suggesting immature to very early oil window thermal maturity. Kerogen types are determined to be dominantly type III, suggesting a dominance of terrestrial input, becoming slightly more mixed type II/III to the southeast. Redox-sensitive trace metals such as uranium, thorium, vanadium, chromium, cobalt, and molybdenum values all suggest a slightly oxygenated sediment water interface during time of deposition. These pyrolysis and trace metal data suggest that the study area was in a prograding proximal marine/prodeltaic depositional environment during Upper Mowry time with influences from higher energy bottom flows. Lateral homogeneity of strata and the low variability in geochemical character across the study area suggest that the local basin in the study area was not segmented by structural or oceanographic conditions. While efforts were made to collect unaltered outcrop samples (digging back into what appeared to be unfractured, unaltered rock), alteration or weathering of organic material is a concern for source rock evaluation of near-surface outcrops. In order to address this concern, a 5-foot-deep trench was dug back into the outcrop at the target horizon in one locality. Samples were taken at regular three-inch intervals from this trench as it was excavated to determine the effect of weathering on TOC in the study area. Based on pyrolysis results, TOC was affected by weathering only along fracture sets (several samples intersected fractures in the shallow subsurface) and did not appreciably increase from the surface to a depth of five feet. Due to the impermeable nature of shale rock, decreases of TOC due to weathering appear to be limited to the immediate surface of samples and along fracture sets.

<p>The results of the multivariate analyses suggest that most of the variation in the composition of the samples was of an intra-sample nature, illustrating large scale patchiness in foraminiferal distribution. There were, however, definite differences between communities around Robben Island and in St Helena Bay, and least variation was found between the control and pipeline sites, and between the stations of each site. When the trace metal concentrations and the percentage nitrogen increased, the richness, diversity and abundance of foraminifera tended to decrease. Sediment grain size positively affected abundance but negatively affected diversity and richness. In both areas mean grain size did not, however, appear to play a very large role in influencing diversity. Cadmium, copper, chromium, the percentage nitrogen and the mean grain size were identified as the most important variables influencing the community structure by the BIOENV BEST routine in PRIMER. The trace metals and percentage nitrogen only had negative effects on the diversity and abundance as well as on the abundance of the dominant genera, whereas the mean grain size had variable effects.</p>

La présente étude porte sur l’évaluation d’une méthode d’acquisition de la solution de sol présente à l’interface sol-racine, dans la rhizosphère. Cette interface constitue le lieu privilégié de prise en charge par les plantes des contaminants, tels que les métaux traces. Comme les plantes acquièrent ces éléments à partir de la phase liquide, la solution de sol de la rhizosphère est une composante clé pour déterminer la fraction de métaux traces biodisponibles. La microlysimétrie est la méthode in situ la plus appropriée pour aborder les difficultés liées à l’échelle microscopique de la rhizosphère. Ainsi, dans les études sur la biodisponibilité des métaux traces au niveau de la rhizosphère, les microlysimètres (Rhizon©) gagnent en popularité sans, toutefois, avoir fait l’objet d’études exhaustives. L’objectif de cette étude est donc d’évaluer la capacité de ces microlysimètres à préserver l’intégrité chimique de la solution, tout en optimisant leur utilisation. Pour ce faire, les microlysimètres ont été soumis à une série d’expériences en présence de solutions et de sols, où la quantité de solution prélevée et le comportement des métaux traces (Cd, Cu, Ni, Pb, Zn) ont été étudiés. Les résultats montrent que les microlysimètres fonctionnent de façon optimale lorsque le contenu en eau du sol est au-dessus de la capacité au champ et lorsqu’il y a peu de matière organique et d’argile. Les sols sableux ayant un faible contenu en C organique reproduisent mieux le volume prélevé et la solution sous la capacité au champ peut être récoltée. L’utilisation des microlysimètres dans ces sols est donc optimale. Dans les essais en solution, les microlysimètres ont atteint un équilibre avec la solution après 10 h de prélèvement. En respectant ce délai et les conditions optimales préalablement établies (pH acide et COD élevé), les microlysimètres préservent la composition chimique de la solution. Dans les essais en sol, cet équilibre n’a pas été atteint après dix jours et huit prélèvements. Le contenu en matière organique et l’activité microbienne semblent responsables de la modification des concentrations en métaux au cours de ces prélèvements, notamment, dans l’horizon FH où les microlysimètres performent très mal. En revanche, dans l’horizon B, les concentrations tendent à se stabiliser vers la fin de la série de prélèvements en se rapprochant des valeurs de référence. Bien que des valeurs plus élevées s’observent pour les microlysimètres, leurs concentrations en métaux sont comparables à celles des méthodes de référence (extrait à l’eau, lysimètres de terrain avec et sans tension). En somme, les microlysimètres se comportent généralement mieux dans l’horizon B. Même si leur utilisation est plus optimale dans un sol sableux, cet horizon est privilégié pour de futures études sur le terrain avec les microlysimètres. / This study focuses on evaluating a method of acquiring soil solution in the soil-root interface of the rhizosphere. The liquid phase of the rhizosphere constitutes the main area where plants absorb contaminants like trace metals. Thus the rhizosphere soil solution is key to determine the amount of bioavailable trace metals. Microlysimetry has been described as the most appropriate in situ method to tackle difficulties inherent to the microscopic scale of the rhizosphere. Despite the lack of an exhaustive evaluation of their performance, microlysimeters have gained popularity for in situ studies on the bioavailability of trace metals. The objective of this study was to evaluate the capacity of microlysimeter to preserve the chemical integrity of the soil solution and also to determine their optimum use conditions. To do this, microlysimeter have been submitted to a series of laboratory experiments with solutions and soils. The volume of solution extracted and trace metals (Cd, Cu, Ni, Pb, Zn) behaviour were studied. Results show that microlysimeters work optimally when soil water content is above field capacity and when the amount of clay and organic matter is low. Sandy soils with low organic carbon content have a better reproducibility for extracted volume and soil solution extraction is possible even when soil water content is below field capacity. Using microlysimeters in this soil type is thus optimal. In solution experiments, microlysimeters reached equilibrium with the control solution after ten hours of extraction. In optimal conditions (acidic pH and high DOC) and after this ten hours period, microlysimeters preserve the chemical composition of the solution. In soil experiments, this equilibrium has not been reached after eight samplings throughout ten days. Organic matter content and microbial activity could be responsible for the modification of concentrations of trace metals during sampling. This is especially true for FH horizon where microlysimeters perform poorly. In contrast, the concentrations reach the reference values toward the end of sampling serie in the B horizon and microlysimeters have a better overall performance in this horizon. Although higher values are observed for microlysimeters, trace metals concentrations are comparable to other extraction methods, specifically for the B horizon. Even if their uses are optimized in sandy soil, the B horizon should be privileged for future field studies involving microlysimeters.

<p>The results of the multivariate analyses suggest that most of the variation in the composition of the samples was of an intra-sample nature, illustrating large scale patchiness in foraminiferal distribution. There were, however, definite differences between communities around Robben Island and in St Helena Bay, and least variation was found between the control and pipeline sites, and between the stations of each site. When the trace metal concentrations and the percentage nitrogen increased, the richness, diversity and abundance of foraminifera tended to decrease. Sediment grain size positively affected abundance but negatively affected diversity and richness. In both areas mean grain size did not, however, appear to play a very large role in influencing diversity. Cadmium, copper, chromium, the percentage nitrogen and the mean grain size were identified as the most important variables influencing the community structure by the BIOENV BEST routine in PRIMER. The trace metals and percentage nitrogen only had negative effects on the diversity and abundance as well as on the abundance of the dominant genera, whereas the mean grain size had variable effects.</p>

Studies have been carried out on specific ion-exchange (Dowex 50W-X8 and Dowex 1-X8) and chelation (Chelex-100) resins, in order to determine their physical and chemical characteristics, to understand and explain their limits of function and to optimise their use as substrates in trace metal and speciation measurement by EDXRF. Structural information was obtained by scanning electron microscopy and x-ray microanalysis showing a homogeneous distribution of functional groups and retained ions on both sectioned and whole resins. Particle size experiments performed on Dowex 50W-X8 (38 - 840 µm) showed that this parameter has no effect on the relationship between intensity of fluorescence and concentration or mass of resin. Inter-element effects were not observed in the analysis of multielemental specimens prepared on ion-exchange / chelation media by EDXRF. This indicates that the proposed method has a significant advantage when compared with other methodologies. A theoretical ‘model’, based on the formation of thin films on the surface of the resin beads, has been proposed in order to link and explain the effects observed in these experiments. The use of a batch retention system has shown distinct advantages over using columns in terms of linearity, accuracy, precision, rapidity and simplicity. Parameters such as pH and ionic strength of the solution, concentration of competing ions and volume of the sample have been proven to be critical. The maximum retention capacity has been determined as 3.2, 1.1 and 0.67 mEq/g for Dowex 50W-X8, Dowex 1-X8 and Chelex-100 respectively. The optimum mass of resin for XRF analysis was found to be 0.5 g, for all resins tested. The linear range covered 4 to 5 orders of magnitude. These findings show the potential of the investigated media to overcome instrumental and sample limitations. Based on the physico-chemical information found, methodologies for three different applications of the resins to EDXRF determinations have been developed and their analytical possibilities explored. The multi-elemental determination of metals in sewage sludge digests was achieved by retaining the metals on Dowex 50W-X8 at pH 2 and Chelex-100 at pH 4. Chelex-100 allows quantitative recoveries for Cu and Zn. A wider range of elements was determined on Dowex 50W-X8, although with poorer recoveries (60 - 90%). The limits of detection were 10 - 21 µg when Dowex 50W-X8 was used and 8 - 49 µg for Chelex-100. The method was validated by the analysis of a certified material. The determination of Kβ/Kα intensity ratios for Cr and Mn species and its potential as a tool for direct elemental speciation has also been studied. A difference in Kβ/Kα between the oxidation states of the analytes was only observed during the analysis of solutions of the metal species by EDXRF at the 98% level of confidence. Finally, the speciation and preconcentration of Cr(III) and Cr(VI) in waters has been performed by retention on Dowex 50W-X8 and Dowex 1-X8 followed by EDXRF determination. Efficient recoveries and preconcentration factors of up to 500 were achieved, leading to limits of detection of 30 µg/L for Cr(VI) and 40 µg/L for Cr(III). This method is simple, fast and inexpensive, allowing quantitative recoveries in the speciation of chromium in waste waters.

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-08-30T17:05:18Z No. of bitstreams: 1 Dissertação - Darlan S Santil.pdf: 1852568 bytes, checksum: 56dd8cda0c9cfac1cef7ea49ee2facfb (MD5) / Approved for entry into archive by Vanessa Reis (vanessa.jamile@ufba.br) on 2016-09-02T15:26:24Z (GMT) No. of bitstreams: 1 Dissertação - Darlan S Santil.pdf: 1852568 bytes, checksum: 56dd8cda0c9cfac1cef7ea49ee2facfb (MD5) / Made available in DSpace on 2016-09-02T15:26:24Z (GMT). No. of bitstreams: 1 Dissertação - Darlan S Santil.pdf: 1852568 bytes, checksum: 56dd8cda0c9cfac1cef7ea49ee2facfb (MD5) / CAPES / O presente estudo propõe a determinação de elementos maiores e traço em invertebrados marinhos por Espectrometria de Emissão Óptica com Plasma Indutivamente Acoplado (ICP OES) após um procedimento assistido por radiação ultrassom e centrífuga, empregando ácidos diluídos. Um planejamento Doehlert de três fatores foi aplicado para otimizar a extração dos elementos nas amostras de bivalves (Mytella guyanensis, Anomalocardia brasiliana e Crassostrea rhizophorae). Os fatores foram: concentração da mistura ácida (HCl + HNO3 + H3CCOOH; 1-3 mol L-1), tempo de centrifugação (10-40 min.), e velocidade de rotação (6000-10000 rpm). A eficiência de extração expressa em percentual foi escolhida como resposta analítica no processo de otimização. Além disso, todos os experimentos foram realizados analisando o material de referência certificado NIST 1566b (tecido de ostra). O percentual de recuperação obtida nas amostras de material de referência certificado pela martiz Doehlert variou de 45-95, 8-52, 35-71, 67-102, 38-78, 61-92, 58-100, 39-85 e 51-91%, respectivamente, para Ca, Cd, Cu, K, Mg, Mn, Na, Sr, e Zn. Todavia, ponto de máximo não foi obtido. Portanto, a resposta múltipla foi escolhida para obtenção dos valores máximos de extração dos metais. As seguintes condições experimentais da resposta múltipla foram selecionadas: 20 min de tempo de extração, 9000 rpm de velocidade de rotação e 1,0 mol L-1 da mistura ácida. A fim de avaliar o efeito do ultrassom na extração dos elementos, uma porção de tecido de ostra certificado foi sonicada por 15 min em um banho de ultrassom à temperatura ambiente e a solução foi centrifugada nas condições otimizadas. Os resultados mostraram que o uso da sonicação antes da centrifugação promoveu um aumento na porcentagem de recuperação dos elementos estudados. A repetitividade do procedimento auxiliado por centrífuga e ultrassom foi avaliada pela determinação de elementos maiores e traço em 10 replicatas do material certificado. Os desvios padrões relativos (RSD) para o procedimento proposto variam entre 1,8 a 4,7. A exatidão do método foi confirmada pela análise de tecido de ostra certificado (NIST 1566b) e por comparação de método analítico de referência com procedimento de digestão ácida para o tratamento das amostras (microondas com cavidade). Os resultaldos da análise da exatidão de alguns elementos estudados mostraram que não havia diferenças significativas (p<0,05) entre o método proposto e o método de referência. Concomitantemente ao desenvolvimento do método analítico, as concentrações dos elementos menores e maiores em amostras dos bivalves coletados ao longo da Baía de Todos os Santos, Bahia, Brasil foram determinadas por ICP OES após o procedimento de digestão ácida em bombas Parr. Os resultados da determinação revelaram que as concentrações de As, Cu e Zn nos bivalves estavam acima dos limites máximos estabelecidos pela ANVISA e por agências especializadas em saúde internacionais. Esses valores de concentração sugerem que deve ser feita uma análise de risco a / The present study proposes the determination of major and trace elements in marine invertebrates by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP OES) after a procedure assisted by ultrasound radiation and centrifugal, employing diluted acids. A three factor Doehlert design was applied to optimize the extraction of elements in bivalves (Mytella guyanensis, Anomalocardia brasiliana and Crassostrea rhizophorae). The factors were: concentration of acid mixture (HCl + HNO3 + H3CCOOH; 1-3 mol L-1), centrifugation time (10-40 min.), and rotation velocity (6000-10000 rpm). The extraction efficiency, expressed as a percentage, was chosen as the analytical response in the optimization process. In addition, all experiments were performed by analyzing the certified reference material NIST 1566b (oyster tissue). The percentage of recovery obtained in the samples of certified reference material by Doehlert varied from 45-95, 8-52, 35-71, 67-102, 38-78, 61-92, 58-100, 39-85 and 51-91%, respectively, for Ca, Cd, Cu, K, Mg, Mn, Na, Sr, and Zn. However, maximum point wasn’t obtained. So, the multiple response was chosen to obtain the maximum extraction of the metals. The following experimental conditions of multiple response were selected: 20 min of extraction time, 9000 rpm of the speed centrifuge and 1.0 mol L-1 of the acid mixture. In order to evaluate the ultrasound effect on the extraction of trace elements a portion of the certified oyster tissue sample was sonicated for 15min in an ultrasonic bath at ambient temperature, and then the solution was centrifuged at the optimized conditions. Results showed that the use of the sonication prior to the centrifugation promoted an increase in the percentage of recovery for most studied elements. The repeatability of the centrifugation and ultra- sound assisted procedure was evaluated by the determination of trace and major elements in 10 replicates of the oyster tissue certified material. The relative standard deviations (RSD) for the centrifugation and ultrasound assisted procedure varied between 1.8 and 4.7%. The accuracy of the method was confirmed by analysis of the certified oyster tissue (NIST 1566b) and by reference analytical method comparison with acid digestion procedure for the sample treatment (microwave cavity). The results of the analysis of the accuracy of some elements studied showed that there were no significant differences (p <0.05) between the proposed method and the reference method. Concurrent with the development of the acid extraction procedure, the major and trace concentrations of elements in mussel, oyster and clams samples collected from along coastal the zones of Todos os Santos Bay were determined by ICP OES after Parr acid digestion bombs. The results of determination showed that concentrations of As, Cu and Zn in the bivalves were above the limits established by ANVISA and international agencies specializing in health. These concentration values suggest that must be a health risk analysis mainly in the communities that collect the shellfish as a subsistence activity.