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Influência do tamanho molecular aparente de substâncias húmicas aquáticas na eficiência da coagulação por hidroxicloreto de alumínio / Influence of apparent molecular size from aquatic humic substances in the efficiency of coagulation by aluminum hydroxychlorideSantos, Camila Tolledo 16 November 2009 (has links)
Estações de tratamento de água que tratam águas com cor elevada, causada pela presença de substâncias húmicas, e baixa turbidez têm apresentado problemas operacionais, principalmente na coagulação. As substâncias húmicas aquáticas (SHA) apresentam moléculas de massa molecular variada, grande parte entre 500 Da e 10 kDa. Por esse motivo, as condições de coagulação (tipo e dosagem de coagulante e pH de coagulação) podem ser totalmente distintas no tratamento de águas com a mesma coloração, devido à presença de SHA com propriedades estruturais diferentes, conforme já observado em pesquisas recentes. Neste contexto, o presente trabalho estudou a influência do tamanho molecular aparente das SHA na coagulação por hidroxicloreto de alumínio e fez a comparação dos custos entre este coagulante e dois estudados anteriormente - sulfato de alumínio e cloreto férrico - para mesma eficiência de remoção de cor. Para isso, realizaram-se ensaios de coagulação seguida de filtração em jarteste com quatro águas de estudo preparadas com frações de diferentes tamanhos moleculares aparentes de SHA, com cor verdadeira de 100 uH e turbidez de 5,0 uT. A partir dos resultados encontrados, pode-se afirmar que há influência do tamanho molecular aparente de diferentes frações de substâncias húmicas aquáticas na coagulação por hidroxicloreto de alumínio. Observou-se a tendência de maior consumo de coagulante para a coagulação de frações de SHA de menores tamanhos moleculares aparentes, em uma faixa determinada de pH. Em relação aos custos, o cloreto férrico foi o coagulante que apresentou menor valor para tratamento (por filtração direta) de águas com elevada cor aparente devida a presença de SHA. / The water treatment plants that treat waters with high brown color caused by the presence of humic substances, and low turbidity have been presenting operational problems, mostly in the coagulation. The aquatic humic substances (AHS) present molecules of different molecular mass, most part between 500 Da and 10 kDa. Therefore, the coagulation terms (coagulant type and dosage and coagulation pH) can be totally distinct in waters treatment with the same coloration, due to the presence of AHS with different structural properties, as already observed in recent researches. In this context, the present work presented the influence of AHS\'s apparent molecular size in the coagulation for aluminum hydroxychloride and did the costs comparison between this coagulant and two studied previously - aluminum sulfate and ferric chloride - for same efficiency of the color removal. For that, it accomplished coagulation rehearsals followed by filtration in jar-test with four waters of study prepared with fractions of different AHS\'s apparent molecular sizes, with true color of 100 uH and turbidity of 5.0 uT. From the found results, it can affirm that there is influence of the apparent molecular size of different fractions from aquatic humic substances in the coagulation for aluminum hydroxychloride. The larger coagulant consumption tendency was observed for the AHS\'s fractions coagulation of smaller apparent molecular sizes, in a range determined by pH. Regarding the costs, the ferric chloride was the coagulant that presented smaller value for treatment (for direct filtration) of waters with high brown apparent color due the presence of AHS.
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Long-term metal retention processes in a peat bog : Field studies, data and modellingSyrovetnik, Kristina January 2005 (has links)
The study was inspired by the need to assess long-term metal retention in municipal solid waste (MSW) landfills. The long-term processes in landfills are poorly known due to the relatively short time that such landfills have been in existence. Natural analogues where similar metal binding processes could be expected were therefore sought for. The work described in this thesis aims to elucidate the long-term transport and attenuation processes involved in the retention of heavy metals in a peat bog, through field studies and modelling. The Oostriku peat bog (central Estonia) has been exposed to metal-rich groundwater discharge over a long period of time and was found to have accumulated high concentrations of Fe, other heavy metals (e.g. Pb, Cu, Zn, Mn), and As. It was characterised in detail with respect to metal depth distribution and main metal binding mechanisms (using an optimised Tessier extraction scheme). The oxidation of metal sulphides in the surrounding carbonate bedrock was proposed to be a possible long-term source of heavy metals in the water emerging in a spring at the peat site. The water in the spring and peat pore-water was sampled and analysed. The dissolution sequence of the sulphide minerals and evolution of the water composition along a flowpath in the carbonate rock were modelled. Resulting aqueous phase concentration of major and minor elements are discussed in relation to governing geochemical processes. The simulated water composition was compared with that observed. Retention of metals transported with water through the peat was assessed through modelling equilibrium sorption on solid organic matter and amorphous ferric oxyhydroxide by using a simplified quantitative modelling approach and independently obtained data. Dynamic evolution of metal sorption fronts along a peat profile over time was modelled to test metal-metal competition effects. A possible formation of ferric oxyhydroxide in the peat bog was also assessed with the model. / QC 20101001
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Untersuchungen zu Eintrag, Verteilung und Verbleib natürlicher organischer Wasserinhaltstoffe aus moorgeprägten Einzugsgebieten von TrinkwasserspeichernFiebiger, Caroline 12 April 2007 (has links) (PDF)
In den letzten 15 Jahren wurde in einigen Mittelgebirgsregionen Zentraleuropas ein regional un-terschiedlich starker Anstieg der Konzentration gelösten organischen Kohlenstoffes (DOC) in Oberflächengewässern festgestellt. Besonders betroffen von dieser Entwicklung sind für die Trink-wasserproduktion genutzte Talsperren. Durch den erhöhten DOC-Gehalt wird die Trinkwasser-aufbereitung nicht nur kostenintensiver, sondern bekommt auch zunehmend Probleme bei der Wahrung der Trinkwasserqualität. Die Quellen des DOC sind in den Einzugsgebieten befindliche Moore und hydromorphe Nassstandorte. Die Ursachen für den in den vergangenen Jahren doku-mentierten Mehraustrag sind äußerst komplex und beinhalten sowohl klimatische als auch nut-zungsbedingte Veränderungen. Ziel der vorliegenden Arbeit ist, den Charakter des DOC näher zu bestimmen, um die für die Wasseraufbereitung problematischen Fraktionen zu benennen und Ansatzpunkte für regulierende Maßnahmen aufzuzeigen. Die Charakterisierung erfolgte an einem LC-OCD-System (Liquid Chromatography – Organic Carbon Detection) am Beispiel der drei Tal-sperrensysteme Muldenberg, Carlsfeld (Westerzgebirge) und Fláje (Osterzgebirge, Tschechien). Die Talsperren weisen unterschiedliche DOC-Gehalte auf. Die Ergebnisse zeigen, dass der DOC aller Untersuchungsgebiete sowohl in den Zuflüssen, dem Talsperrenwasser bzw. Rohwasser als auch dem Reinwasser der Wasserwerke von Huminstoffen dominiert wird. DOC-Schwankungen sind folglich auf Schwankungen der Huminstoffkonzentrationen zurückzuführen. In den Zuflüs-sen treten die höchsten Huminstoffkonzentrationen während der Schneeschmelze im Frühjahr und bei Starkniederschlägen im Sommer und Herbst auf. Niedrige Konzentrationen sind an Bo-dengefrornis oder Trockenphasen im Sommer gebunden. In den Talsperren tritt im Sommer eine Schichtung der Huminstoffe auf, bei der an der Oberfläche durch photolytischen Abbau niedrige-re Konzentrationen und in Abhängigkeit von der Talsperrentiefe durch die Einschichtung der Zuflüsse am Grund höhere Konzentrationen auftreten. Die Verteilung im Winter ist allein von der Einschichtung der Zuflüsse abhängig. Die Verteilung der Building Blocks (Huminstoffhydrolysate) ist im Sommer der der Huminstoffe entgegengesetzt, da sich beim photolytischen Abbau von Hu-minstoffen Building Blocks bilden. Während der Zirkulationen sind die Konzentrationen der Hu-minstofffraktionen im gesamten Tiefenprofil gleich. In den Talsperren Muldenberg und Carlsfeld wurde im Untersuchungszeitraum unter Berücksichtigung der technischen Gegebenheiten und anderer Wassergütekriterien der optimale Rohwasserentnahmehorizont (niedrigstmögliche Hu-minstoffkonzentration) gewählt. In der Talsperre Fláje könnte die Rohwasserqualität durch Instal-lation eines schwenkbaren Entnahmerohres erheblich verbessert werden. In den Wasserwerken sind die Huminstofffraktionen mit abnehmender Molekülgröße schwieriger zu entfernen. Die relativ niedermolekularen Building Blocks sind die am schwersten entfernbaren DOC-Bestandteile. Auf Grundlage mathematischer Beziehungen zu SAK254 bzw. DOC wurde ein Programm (DOCQuaC – DOC-Quality Calculator) entwickelt, mit dessen Hilfe die Huminstofffraktionen über diese Grundparameter ermittelt werden können. Neben der Fraktionsquantifizie-rung besteht im Programm die Möglichkeit zur Berechnung der Eliminierungsleistung, so dass beispielsweise nach der Durchführung einer Maßnahme zur Verbesserung der DOC-Entfernung eine unmittelbare Aussage über den Effekt auf die Fraktionen vorliegt. / For the last 15 years a change of Dissolved Organic Carbon (DOC) has been taking place in surface waters of Middle European Highlands. The degree of this increase is regionally dependent. The reasons as well as the consequences of this development are of high complexity. The changes are expressed in an increase of middle DOC values and, additionally, an increase of annual changes. Reservoirs, used for drinking water production, are particularly affected, because the heightened DOC content increases the costs for drinking water treatment, and currently it is not possible to maintain a good drinking water quality. The main DOC source are peat bogs, situated in the catchments. The cause of the increasing DOC output from peat bogs are very complex and contain changes as well in climate as in land use. The aim of this presented dissertation was to gain more information about the character of DOC, so that those fractions can be determined which are problematically to remove inside the waterworks. On that base it should be possible to find some starting points for more regulating measures. The analytical characterisation was carried out by the help of a LC-OCD-System (Liquid Chromatography – Organic Carbon Detection), exemplary for the reservoir systems Muldenberg, Carlsfeld (Western Ore Mountains) and Fláje (Eastern Ore Mountains, Czech Republic). Although the DOC concentrations are very different in the reser-voirs, it was always dominated by humic substances, namely as well in the tributaries, as in the raw and treated water. Thus changes in the DOC concentration are due to changes in the concen-tration of humic substances. In spring and summer occur the highest concentrations of humic substances in the tributaries. Low concentrations are linked with frost in winter or dry periods in summer. In the reservoirs in summer a stratification of humic substances shapes up, with lower concentration near the water surface (caused by photolytical degradation) and accordingly higher concentration near the ground (layering of influxes). Distribution in winter only depends on the layering of the influxes. In summer the concentration of Building Blocks (humic substance hydro-lysates) is opposite to that of humic substances, because of the creation of Building Blocks at the photolytical degradation. During circulation the concentration of all humic substance fractions are equal in each reservoir layer. In the reservoirs Muldenberg and Carlsfeld, a further optimisation of the raw water withdrawal horizon is not possible. In the reservoir Fláje the raw water could be much improved by installing a movable withdrawal device. With decreasing molecular size the elimination of the humic fractions gets more difficult in the waterworks. Most difficult to eliminate are Building Blocks. On the basis of the mathematical cor-relation between humic fractions and the SAC254 and DOC a program (DOCQuaC – DOC-Quality Calculator) has been developed, which enables die calculation of humic concentrations by enter-ing these general parameters. In addition to the calculation of the concentrations it is possible to calculate the elimination capacity for the humic fractions. Thus the effects of measures on the humic fractions, which could be done for optimisation of the elimination capacity, can be imme-diately observed.
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Investigation of the Complexation and the Migration Behavior of Actinides and Non-Radioactive Substances with Humic Acids under Geogenic Conditions - Complexation of Humic Acids with Actindies in the Oxidation State IV Th, U, NpBernhard, Gert, Schmeide, Katja, Sachs, Susanne, Heise, Karl-Heinz, Geipel, Gerhard, Mibus, Jens, Krepelova, Adela, Brendler, Vinzenz 31 March 2010 (has links) (PDF)
Objective of this project was the study of basic interaction and migration processes of actinides in the environment in presence of humic acids (HA). To obtain more basic knowledge on these interaction processes synthetic HA with specific functional properties as well as 14C-labeled HA were synthesized and applied in comparison to the natural HA Aldrich. One focus of the work was on the synthesis of HA with distinct redox functionalities. The obtained synthetic products that are characterized by significantly higher Fe(III) redox capacities than Aldrich HA were applied to study the redox properties of HA and the redox stability of U(VI) humate complexes. It was confirmed that phenolic OH groups play an important role for the redox properties of HA. However, the results indicate that there are also other processes than the single oxidation of phenolic OH groups and/or other functional groups contributing to the redox behavior of HA. A first direct-spectroscopic proof for the reduction of U(VI) by synthetic HA with distinct redox functionality was obtained. The complexation behavior of synthetic and natural HA with actinides (Th, Np, Pu) was studied. Structural parameters of Pu(III), Th(IV), Np(IV) and Np(V) humates were determined by X-ray absorption spectroscopy (XAS). The results show that carboxylate groups dominate the interaction between HA and actinide ions. These are predominant monodentately bound. The influence of phenolic OH groups on the Np(V) complexation by HA was studied with modified HA (blocked phenolic OH groups). The blocking of phenolic OH groups induces a decrease of the number of maximal available complexing sites of HA, whereas complex stability constant and Np(V) near-neighbor surrounding are not affected. The effects of HA on the sorption and migration behavior of actinides was studied in batch and column experiments. Th(IV) sorption onto quartz and Np(V) sorption onto granite and its mineral constituents are affected by the pH value and the presence of HA. HA exhibits a significant influence on the transport of U(IV) and U(VI) in a laboratory quartz sand system. In order to provide the basis for a more reliable modeling of the actinide transport, the metal ion complexation with HA has to be integrated into existing geochemical speciation codes. Within this project the metal ion charge neutralization model was embedded into the geochemical modeling code EQ3/6. In addition to that, a digital data base was developed which covers HA complexation data basing on the charge neutralization model.
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Étude des interactions du Benzo(a)pyrène avec les trois fractions physiques de la matière organique du sol par matrices d'excitation et d'émission de fluorescence couplées à PARAFAC / Study of the interactions of Benzo(a)pyrene with the three physical fractions of soil organic matter by means of fluorescent excitation and emission matrices coupled to PARAFACEl Fallah, Rawa 15 December 2017 (has links)
Les propriétés spectrales des composants fluorescents de la matière organique d’un sol naturel ont été étudiées dans les trois fractions physiques ; substances humiques, acide fulvique et acide humique, par la méthode des matrices d’excitation et d’émission de fluorescence couplée à l’algorithme Parallel Factor analysis (PARAFAC). Les modifications spectrales de ces composants ont été suivies (forme et pseudo-concentrations) en présence d’un contaminant de type hydrocarbure aromatique polycyclique (le benzo(a)pyrène (BaP), toxique et à caractère cancérigène) : (1) en faisant varier les volumes d’une solution pure de BaP dans chaque fraction de même concentration en matières organiques, (2) en faisant varier les concentrations en matière organique pour des concentrations fixes de BaP, qui ont été suivies dans le temps. Les résultats ont montré que le BaP influence d’une manière différente les fluorophores présents dans les trois fractions et ont permis de clarifier le type d’interactions avec une fraction ou l’autre. D’autre part, une discussion a été menée sur les paramètres de validation du nombre de composants pour le choix des modèles de PARAFAC. / The spectral properties of the fluorescent components of the organic matter of a natural soil were studied in the three physical fractions; humic substances, fulvic acid and humic acid, by the method of the excitation and fluorescence emission matrices coupled to the Parallel Factor Analysis (PARAFAC) algorithm. The spectral modifications of these components were studied (form and pseudo-concentrations) in the presence of a polycyclic aromatic hydrocarbon contaminant (benzo (a) pyrene (BaP), toxic and carcinogenic): (1) by varying the volumes of a pure solution of BaP in each fraction having the same concentration of organic matter, (2) by varying the concentrations of organic matter for fixed concentrations of BaP, which were followed over time. The results showed that the BaP influences the fluorophores present in the three fractions in a different way and clarified the type of interactions with one fraction or the other. On the other hand, a discussion was held on parameters for validating the number of components for the selection of PARAFAC models.
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Studie možnosti ovlivnění procesu transformace primární organické hmoty v kompostu ionty Ca+2 a Mg+2HÁJEK, František January 2017 (has links)
This study focuses on the entire proces of composting. It begins with listing the attributes of entry materials and spans to outlining the creation of characteristic substances in the compost (humus). Problems and solutions relating to determining the quality and quantity of humus in the compost are elaborated. This thesis was designed to identify efficient compost accelerator additives for gardening composts.
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Vliv huminové látky HS 1500 na toleranci jesetera malého vůči dusitanům / Influence of humic substance HS 1500 on tolerance of Sterlet to nitriteBULÍČEK, Vojtěch January 2014 (has links)
The aim of the thesis was to assess the effect of humic substance HS 1500 on the tolerance of Sterlet (Acipenser ruthenus) to nitrite. Preparation Huminfeed was used as a source of substance HS 1500. Tolerance of Sterlet to nitrite was assessed on the basis of the results of acute toxicity tests and the results of haematological and biochemical blood examination of fish that were exposed to increased concentrations of nitrite in the presence and absence of preparation Huminfeed.
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Relações da matéria orgânica com a hidrofobicidade do solo / Relationship of organic matter with soil hydrophobicityVogelmann, Eduardo Saldanha 14 July 2014 (has links)
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Soil hydrophobicity can be conceptually defined as soil repellency to water and is associated with the covering of soil particles by hydrophobic organic substances which interact with mineral particles and pores in a complex way, making soil wetting difficult. The objectives of this study were to: (i) determine the biochemical composition of vegetation, physical and chemical properties of soil organic matter fractions and their relationships to the occurrence and degree of soil hydrophobicity; (ii) analyze the effects of hydrophobic compounds at different intensities on sorptivity and water retention curve; (iii) measure and monitor the effects of variation of soil temperature and water content on the variability of the degree of soil hydrophobicity during a drying cycle. Soil samples were collected from different soil classes in the Rio Grande do Sul and Santa Catarina States, southern Brazil. From the 0-5, 5-10 and 10-15 cm soil layers, undisturbed samples (in blocks) were collected for the determination of sorptivity while preserved samples were collected using core samplers (volume of 47 cm³) for the evaluation of water retention curve, soil bulk density, total porosity, macroporosity and microporosity. From these layers, deformed samples were also collected for soil chemical and physical characterization. However, part of the samples used for the determination of water retention curves were previously subjected to sequential chemical extraction with acetone and a solution of isopropanol:ammonia to remove hydrophobic compounds. Soil carbon analysis consisted of determination of total organic carbon, physical (> 53μm and <53μm), and chemical (fulvic and humic acids and humin) fractions. Water and ethanol sorptivity was determined using tension micro-infiltrometer. Hydrophobicity was evaluated by comparing water and ethanol sorptivity values and soil-water contact angle was calculated from the hydrophobicity index. The effect of temperature was measured using PVC cylinder (785 cm³) constructed with disturbed samples from different soils, wetted and dried under different temperatures (20, 45 and 70 °C) and the hydrophobicity was determined using the water droplet penetration time method. Hydrophobicity had an intimate relationship with soil organic carbon content, mainly organic compounds accumulated in physical fractions <53 μm and chemical fraction humin, indicating that hydrophobic compounds are highly recalcitrant and are strongly associated with silt and clay fractions, forming stable organo-mineral complexes, and at the same time, covering all or part of surfaces of mineral particles or aggregates. The existence of these hydrophobic compounds caused changes in sorptivity and soil-water contact angle, directly affecting capillary and soil water retention curve, and reduced the volume of water retained at lower potentials. The heating of the soil at temperatures at or below 45 °C did not alter the intensity of hydrophobicity but there were changes when soil temperature exceeded 70 °C or when the soil moisture was drastically reduced. / A hidrofobicidade do solo pode ser conceitualmente definida como a repelência do solo à água e está associada ao recobrimento das partículas do solo por substâncias orgânicas hidrofóbicas, que interagem de forma complexa com os poros e partículas minerais, dificultando o molhamento do solo. Os objetivos deste trabalho foram: (i) determinar a composição bioquímica da vegetação, das frações físicas e químicas da matéria orgânica e suas relações com a ocorrência e grau de hidrofobicidade; (ii) analisar os efeitos dos compostos hidrofóbicos em diferentes intensidades na sortividade e na curva de retenção de água; (iii) avaliar e monitorar os efeitos da variação da temperatura e do conteúdo de água na variação do grau de hidrofobicidade do solo ao longo de um ciclo de secagem. Foram coletadas amostras de solo de diferentes classes de solos existentes no Estado do Rio Grande do Sul e Santa Catarina. Nas camadas de 0 5, 5 10 e 10 15 cm foram coletadas amostras indeformadas (blocos), para a avaliação da sortividade e amostras com estrutura preservada, com cilindros metálicos (47 cm³), para a determinação da curva de retenção de água, densidade do solo, porosidade total, macroporosidade e microporosidade. Nessas camadas também foram coletadas amostras deformadas para a caracterização química e física dos solos. No entanto, parte das amostras utilizadas na determinação da curva de retenção de água foram previamente submetidas a uma extração química sequencial com acetona e uma solução de isopropanol:amônia para remoção dos compostos hidrofóbicos. A análise do carbono constou da determinação do carbono orgânico total e da determinação das frações físicas (>53μm e <53μm) e químicas (Ácidos Fúlvicos, Ácidos Húmicos e Humina). A sortividade da água e do etanol foram determinadas com um micro-infiltrômetro de tensão. A hidrofobicidade foi avaliada comparando valores de sortividade da água e do etanol. O ângulo de contato água-solo foi calculado a partir do índice de hidrofobicidade. O efeito da temperatura foi mensurado em cilindros de PVC (785 cm³) construídos com amostras desagregadas dos diferentes solos. As amostras foram umedecidas e secas sob diferentes temperaturas (20, 45 e 70°C), sendo a hidrofobicidade determinada simultaneamente pelo método do tempo de penetração da gota de água. A hidrofobicidade apresentou uma íntima relação com o teor de carbono orgânico do solo, principalmente com os compostos orgânicos acumulados na fração física <53 μm e na fração química da Humina, indicando que os compostos hidrofóbicos provavelmente apresentam elevada recalcitrância e estão fortemente associados às frações silte e argila, formando complexos organo-minerais estáveis, ao mesmo tempo em que recobrem total ou parcialmente a superfície de agregados ou partículas minerais. A existência desses compostos hidrófobos causa alterações na sortividade e no ângulo de contato água-solo, afetando diretamente a capilaridade e a curva de retenção do solo, reduzindo o volume de água retido nos menores potenciais. O aquecimento do solo à temperaturas inferiores a 45 °C não causa modificações na intensidade da hidrofobicidade, que é alterada somente quando a temperatura do solo excede a 70 °C ou quando a umidade do solo é acintosamente reduzida.
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Distribuição, complexação e mobilidade de íons arsênio em águas superficiais do Quadrilátero Ferrífero-MG/Brasil: ênfase nas interações com substâncias húmicas aquáticas / Distribution, complexation and mobility of arsenic ions in surface waters from Quadrilátero Ferrífero-MG/Brazil: emphasis on interactions with aquatic humic substancesGontijo, Erik Sartori Jeunon [UNESP] 27 March 2017 (has links)
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Previous issue date: 2017-03-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Deutscher Akademischer Austauschdienst (DAAD) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O As está distribuído em diversas formas químicas em sistemas aquáticos, o que determina o seu comportamento e destino no ambiente. Nesse contexto, as substâncias húmicas (SH) têm um importante papel por serem capazes de complexar esse metaloide e alterar sua mobilidade e biodisponibilidade. O Fe também tem grande importância por poder formar complexos ternários SH-Fe-As. Apesar da química do As já ter sido bem estudada, o seu comportamento em ambientes ricos em SH e Fe ainda não é totalmente compreendido. Os objetivos desse trabalho foram investigar a distribuição do As, Al e Fe em águas superficiais de uma região mineira no sudeste do Brasil (Quadrilátero Ferrífero, QF) e entender como características de SH extraídas de diferentes regiões (Brasil e Alemanha) afetam a complexação do As(V) na presença de Fe(III). Amostras de águas foram coletadas em 12 pontos do QF, filtradas (0,45 µm) e ultrafiltradas (1 kDa) para separar as frações particulada (>0,45 µm), coloidal (<0,45 µm e >1 kDa) e livre (<1 kDa) de As, Al e Fe. A técnica de difusão em filmes finos por gradientes de concentração (DGT) foi usada em 5 dos 12 pontos para estudar a fração lábil dos elementos estudados. Carbono orgânico total (COT) e dissolvido (COD) também foram medidos. SH foram extraídas de quatro pontos (um no Brasil nas estações seca e chuvosa e três na Alemanha) para testar a influência de diferentes tipos de SH e Fe(III) na complexação do As(V). As SH foram caracterizadas e foram feitos testes de complexação utilizando sistema de ultrafiltração com membrana de 1 kDa. Todos os dados foram analisados pela rede neural de Kohonen. Os resultados mostraram que a maior parte do Al e Fe total no QF estava presente na fração particulada e o As na fração livre. A maior parte do Al e Fe dissolvido estava na fração coloidal e inerte, diferente do As que era mais lábil e potencialmente biodisponível. A maioria das amostras apresentou comportamento similar nas estações seca e chuvosa no QF. Diferenças entre os resultados de ultrafiltração e DGT foram atribuídos a distinções metodológicas e processos químicos. Os resultados de caracterização dos extratos mostraram que a maior parte do As e Fe estavam predominantemente nas frações de maior tamanho molecular. Todos os extratos de SH complexaram quantidades similares de As(V) nos testes de complexação, exceto o extrato do rio Selke, onde foi encontrado menos As(V) livre (mais complexado). Essa diferença foi atribuída ao S e à grupos N-C aromático na estrutura de SH. Isso reforça que a qualidade das SH é um importante fator capaz de influenciar o comportamento do As em ambientes ricos em matéria orgânica e Fe, que também pareceram ser fatores limitantes nas interações com o As. A rede neural de Kohonen foi uma ferramenta importante nas investigações de distribuição do As e complexação do As(V) por Fe(III) e SH. / As is distributed in different chemical forms in aquatic systems. These different forms control its behaviour and fate in the environment. The humic substances (HS) have an important role in the As cycle since they can complex this metalloid and change its mobility and bioavailability. Fe is also important because it can form ternary complexes HS-Fe-As. Although the As chemistry is well studied, the behaviour of As in HS and Fe-rich environments is not totally known. This thesis aimed to investigate the distribution of As, Al and Fe in surface waters from a mining region in the southeast of Brazil (Quadrilátero Ferrífero, QF) and understand how characteristics of HS extracted from different regions (Brazil and Germany) affect the complexation of As(V) in the presence of Fe(III). Water samples were taken in 12 points in QF, filtered (0.45 µm) and ultrafiltered (1 kDa) to separate the fractions particulate (>0.45 µm), colloidal (<0.45 µm and >1 kDa) and free (<1 kDa) of As, Al and Fe. The technique of diffusive gradients in thin films (DGT) was used in 5 of the 12 points to study the labile fraction of the elements studied. Total organic carbon (TOC) and dissolved organic carbon (DOC) were also measured. HS were extracted from four points (one in Brazil in dry and rainy seasons and three in Germany) to analyse the influence of HS from different origins and Fe(III) on the complexation of As(V). The HS were characterised and complexation experiments were performed using an ultrafiltration system with 1 kDa membrane. All data were analysed using the Kohonen neural network. The results showed that most of total Al and Fe in QF was in the particulate fraction and As was in the free fraction. Most of the dissolved Al and Fe was in the colloidal and inert fraction, while As was more labile and potentially more bioavailable. Most samples had similar behaviour in the dry and rainy seasons in the QF. Differences between results of ultrafiltration and DGT were attributed to methodological distinctions and chemical processes. The results of characterisation of extracts showed that most of As and Fe was in the fractions of higher molecular size. All HS extracts complexed similar amounts of As(V), except Selke, where a lower amount of free As(V) was detected (more complexed). This difference was attributed to S and N-aromatic C groups in HS structure. It supports that the quality of HS is an important factor able to influence the behaviour of As in environments rich in organic matter and Fe. The Kohonen neural network was an important tool in the investigation of the distribution of As and As(V) complexation by Fe(III) and HS. / FAPESP: 2012/17727-8
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Determinação de subprodutos clorados formados durante a etapa de oxidação da água contendo substâncias húmicas / Determination of chlorine by-products wich have been formed during the water oxidation step with humic substancesSérgio Marcos Sanches 30 March 2005 (has links)
No Brasil, a desinfecção e oxidação da água, para o consumo humano, são usualmente realizadas com a adição de cloro nas formas de gás cloro e hipoclorito de sódio. Estudos recentes tem demonstrado que a oxidação e desinfecção da água com o cloro podem ocasionar a formação de trialometanos e outros subprodutos clorados. Alguns destes subprodutos são substâncias carcinogênicas. Neste trabalho estudou-se a influência das substâncias húmicas (SH) extraídas da turfa, com diferentes massas moleculares, na formação de trialometanos e outros subprodutos clorados em decorrência do uso do cloro e dióxido de cloro na etapa de oxidação da água. As frações das SH utilizadas neste trabalho foram caracterizadas por análise elementar, ultravioleta visível, ressonância magnética nuclear de C13 (RMN de C13), ressonância paramagnética nuclear eletrônica (EPR) e infravermelho. Estas caracterizações demonstraram que a fração de menor massa molecular (30-100 KDa), obtidas por ultrafiltração (UF), apresentou um menor grau de condensação de grupamentos aromáticos em relação as frações de SH de massa molecular menor que 0,45 μm e maior do que 100 KDa. Nas análises realizadas por RMN de C13 e análise elementar, constatou-se que a fração de SH de massa molecular entre 30-100 KDa, apresentou uma maior porcentagem de grupos contendo oxigênio. Após as caracterizações das SH, preparou-se três tipos de água, com cor 100 +/ - 5 uH, adicionando-se as diferentes frações de SH na água separadamente. A seguir foram realizados ensaios no equipamento jarteste, para a determinação das dosagens dos oxidantes cloro e dióxido de cloro os quais foram utilizadas nos ensaios de formação dos subprodutos clorados. Estes ensaios foram realizados variando-se as dosagens do oxidante em função do tempo de reação. As concentrações dos oxidantes determinadas foram de 7,0 mg/L para o cloro e de 1,0 mg/L para o dióxido de cloro. Na realização dos ensaios de formação dos subprodutos clorados, considerou-se o tempo de reação em função da dosagem dos oxidantes cloro e dióxido de cloro que foram determinadas anteriormente nos ensaios de demanda. Os subprodutos clorados, formados, foram quantificados utilizando-se a técnica de cromatografia gasosa com detector de captura de elétrons. O método utilizado foi o do padrão interno. O clorofórmio foi o subproduto majoritário, nos ensaios realizados com todas as frações. Na oxidação da água com o cloro, ocorreu a formação de um maior número de subprodutos clorados em relação aos ensaios realizados com oxidante dióxido de cloro. Nos ensaios realizados com a água preparada com SH de menor tamanho molecular ocorreu uma maior concentração dos subprodutos clorados formados, especialmente para o clorofórmio. / In Brazil, the disinfection and oxidation of drinking water is usually done by the addition of chlorine gas and sodium hypochloride forms. Recent studies have demonstrated that disinfection and oxidation of water using chlorine can cause the formation of trihalomethane and others chlorine by-products, which are carcinogenic substances. In this present work, it has been studied the influence of the humic substance (SH) extracted from peat soil, with different molecular size, in the formation of trihalomethane and others chlorine by-products as results of the use of chlorine and chlorine dioxide in the water oxidation step. The SH fractions used in this were characterized by elemental analysis, visible ultraviolet, C13 nuclear magnetic resonance (C13 NMR), electron paramagnetic resonance (EPR) and infrared spectroscopy. Such characterization showed that the fractions with smaller molecular size (30-100 KDa), obtained by ultrafiltration (UF), presented a smaller degree of aromatic groups condensation with respect to fractions of SH molecular size smaller than 0,45 μm and higher than 100 KDa. C13 NMR and elemental analysis were also used. SH fraction of molecular size between 30-100 KDa presented higher percentage of groups containing oxygen. After characterizations of SH, water was prepared with 100 +/- 5 uH color, with separated addition of different fractions of SH in the water. Tests in the jartest equipment were realized for the determination of dosages of chlorine and chlorine dioxide oxidants, which were utilized in the test of formation of chlorine by-products. These tests were performed studying the oxidation dosage in function of the reaction time. The oxidant concentrations were 7.0 mg/L for the chlorine and 1.0 mg/L for chlorine dioxide. Formation of chlorine by-products was tested considering the reaction of time with respect to the oxidants dosage of chlorine and oxidant chlorine, previously determined. The chlorine by-products resultant were quantified using the gas chromatography with detector of electron capture technique GC-ECD. The method utilized was the addition of internal standard. In the water oxidation by chlorine an higher number of chlorine by-products occurred in comparison of the test performed with chlorine dioxide. In the test performed with the water prepared with SH of smallest molecular size a highest concentration of resultant by-products occurred, specially by chloroform.
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