The interaction behavior of humic acids with uranium(VI) and the influence of humic substances on the migration behavior of uranium was investigated. A main focus of this work was the synthesis of four different humic acid model substances and their characterization and comparison to the natural humic acid from Aldrich. A radiometric method for the determination of humic acid functional groups was applied in addition to conventional methods for the determination of the functionality of humic acids. The humic acid model substances show functional and structural properties comparable to natural humic acids. Modified humic acids with blocked phenolic OH were synthesized to determine the influence of phenolic OH groups on the complexation behavior of humic acids. A synthesis method for 14C-labeled humic acids with high specific activity was developed. The complexation behavior of synthetic and natural humic acids with uranium(VI) was investigated by X-ray absorption spectroscopy, laser-induced fluorescence spectroscopy and FTIR spectroscopy. The synthetic model substances show an interaction behavior with uranium(VI) that is comparable to natural humic acids. This points to the fact that the synthetic humic acids simulate the functionality of their natural analogues very well. For the first time the influence of phenolic OH groups on the complexation behavior of humic acids was investigated by applying a modified humic acid with blocked phenolic OH groups. The formation of a uranyl hydroxy humate complex was identified by laserspectroscopic investigations of the complexation of Aldrich humic acid with uranium(VI)at pH 7. The migration behavior of uranium in a sandy aquifer system rich in humic substances was investigated in column experiments. A part of uranium migrates non-retarded through the sediment, bound to humic colloids. The uranium migration behavior is strongly influenced by the kinetically controlled interaction processes of uranium with the humic colloids. The influence of humic acids on the sorption of uranium(VI) onto phyllite was investigated in batch experiments using two different humic acids. The uranium(VI) sorption onto the rock phyllite is influenced by the pH-dependent sorption behavior of the humic acids.

The diploma thesis is focused on the study of interactions between biopolymers and model probes in a hydrogel media utilizing diffusion processes. The main aim was to test and to optimize selected combination of diffusion methods (diffusion cells and unsteady diffusion) in study of interactions between biopolymers and organic dyes. Anionic (humic acids) and cationic (chitosan) representatives of biopolymers were utilized and methylene blue and methylene orange were used as a reactivity probe in the case of humic acids and chitosan, respectively. Another appreciable part of the work is represented by in-depth characterization of applied biopolymers and hydrogel samples by a wide range of analytical and physico-chemical methods (rheometry, UV-VIS, FT-IR etc.). Besides particular experimental results on studied systems, the diploma thesis provides both theoretical and practical background for subsequent applications of the innovative and full-automated method for reactivity mapping of biopolymers.

No description available.

No description available.

Os solos têm um importante papel na maioria das atividades que ocorrem no planeta, dentre as quais, destaca-se a sua participação nos principais ciclos biogeoquímicos. A matéria orgânica do solo (MOS) tem um papel primordial na sustentabilidade ambiental, pois está relacionada com a ciclagem de carbono e nutrientes, sendo assim uma figura chave tanto para estudos relacionados com mudanças climáticas globais, quanto para estudos agronômicos. Um dos principais fluoróforos da MOS são as substâncias húmicas (SH), as quais são fracionadas de acordo com a sua solubilidade em ácidos húmicos (AH), ácidos fúlvicos (FA) e humina (HU). O estudo das propriedades ópticas da matéria orgânica é uma importante ferramenta para a compreensão estrutural e molecular das frações húmicas. Frente ao exposto, esse trabalho teve com objetivo estudar a gêneses de Espodossolos Amazônicos através da avaliação das características estruturais da matéria orgânica e suas propriedades de complexação com metais empregando diversas técnicas espectroscópicas. Os resultados mostraram grandes acúmulos de carbono em profundidade e que a Matéria Orgânica nesses Espodossolos Amazônico é constituída de quatro grupos: - mais recalcitrante, humificada e antiga; - lábil e jovem; - recalcitrante, pouco humificada e antiga; - humificada e jovem. Claramente o trabalho mostrou que o processo de humificação não tem relação direta com a datação do material orgânico, e que fatores como textura, presença de água e microorganismos influenciaram nos processos de formação e humificação desse material orgânico. Por fim, a fração AF do solo parece ter uma contribuição oriunda de lençóis freáticos, sua estrutura química varia pouco no perfil e possui seletividade na interação com os metais presentes nesses solos. Basicamente, o AF tem alta afinidade de complexação com Al. A fração AH, entretanto, mostrou-se menos seletiva, associando-se com vários tipos de metais, como K, Fe, Mg, Zn e Al; e sua estrutura química varia bastante no perfil do solo. Em função da diversidade de metais associados ao AH, ele deve ser o principal responsável pela fertilidade do solo. Desta forma, os resultados mostraram que as três frações húmicas estão envolvidas no processo de podzolização do solo, e que o AF tem papel predominante no transporte de Al e o AH é o responsável no transporte do Fe. / Soils play an important role in most of the activities that occur on the planet. It participation in the main biogeochemical cycles can be highlighted. Soil organic matter (SOM) plays a key role in environmental sustainability, since it is related to carbon and nutrient cycling, being essential for studies related to global climate change and agronomy. One of the major SOM fluorophore is the humic substances (HS), which is fractionated according to their solubility in humic acids (HA), fulvic acids (FA) and humin (HU). The study of the optical properties of the organic matter is an important tool for structural and molecular understanding of humic fractions. Based on that, this work aimed the study of the Amazonian Spodosols genesis through the evaluation of organic matter structural characteristics and its properties of metal complexation using different spectroscopic techniques. The main results of this research showed large carbon accumulations in depth. Furthermore, it was possible to infer how the Amazonian Spodosols organic matter is divided: - more recalcitrant, humified and old; - labile and young; - recalcitrant, little humified and old; - humified and young. The study demonstrated clearly that the humification process has no direct relationship with the organic material dating, and that factors such as texture, presence of water and microorganisms have influenced the formation and humification of that organic material. The FA fraction of the soil has a contribution from groundwater and its chemical structure varies little in depth. Additionally, FA showed selective interaction with soil metals. However, the HA fraction has been shown less selective, associate with various metal types, such as K, Fe, Mg, Zn and Al. Moreover, its chemical structure varies greatly in the soil depth. Due to the diversity of metals that the HA has affinity, it should be the main responsible of the soil fertility. After all, the results showed that all the three humic fractions are involved in the process of soil podzolization. Furthermore, the FA has a predominant role in Al transport as the HA is the responsable of Fe transport.

[pt] Este trabalho tem como objetivo principal utilizar um rejeito do processo de concentração de carvão mineral (RJ) como fonte de substâncias húmicas, em particular, do ácido húmico (AH). Para atingir o objetivo a pesquisa foi dividida em três etapas: a obtenção, a caracterização e a aplicação do AH. Na primeira etapa, foram utilizados três métodos diferentes de funcionalização da amostra: o processo químico (PQ), a eletrólise (ELE) e o uso de autoclave (PRESS), previamente ao procedimento de extração das substâncias húmicas (SH), em particular, do ácido húmico (AH). Observou-se que, em termos de recuperação em massa nas condições operacionais estabelecidas, o método de processo químico (PQ) foi o mais eficiente resultando 20,2 porcento de AH e 3,8 porcento para AF-Like. Na segunda etapa, estudou-se a caracterização química (acidez fenólica, acidez total, acidez pelos grupos carboxílicos, pH, CTC e cinza), espectroscópica (FTIR, RMN de 13C e ICP-OES), análise elementar, análise térmica (TGA) e análise estrutural (MEV - EDS) dos ácidos húmicos produzidos. Observou-se certa semelhança entre os AH s extraídos do solo e o AH obtido neste trabalho, com a diferença deste ser muito aromático, o grau de aromaticidade mostrou-se muito elevado (em torno de 60 porcento em relação a 15 porcento do solo). Além disso, as características em relação ao CTC foram relevantes, pois variou de 22 a 44 Cmolckg elevado a -1. Este valor é considerado moderadamente alto em relação ao valor médio de 25 Cmolckg elevado a -1 do CTC, oriundo dos solos brasileiros. Os resultados obtidos por espectroscopia de FTIR e de RMN de 13C indicaram que a funcionalização do rejeito de carvão mineral (RJ) por qualquer um dos métodos de obtenção é relativamente baixa (de 5,0 a 9,7 porcento C-carboxílico) em comparação aos AH proveniente dos solos. Os resultados comparativos apresentaram similaridade nas características estruturais e físicas, observadas pela microscopia eletrônica de varredura. Na terceira etapa foi realizado um estudo preliminar sobre a capacidade do AH, obtido pelo método PQ de reter o chumbo, contido em solução sintética (1000 mgL elevado a -1). Constatando-se uma eficiência de 98 porcento na adsorção deste elemento quando se utilizou uma razão de 1:1(1g AH:1g Pb) e vazão de 0,06 mL/min. / [en] This work aims to evaluate the use of a concentration coal tailing (RJ) as a source of humic substances, particularly humic acid (HA). To achieve the goal the research was divided into three steps: obtaining, characterization and application of HA.In the first step three different methods of functionalization of the sample were tested prior to the HA extraction procedure: chemical process (PQ), electrolysis (ELE) and the using of an autoclave (PRESS). It was observed that in terms of mass recovery and within established operating conditions, the method of chemical process (PQ) result was the most efficient, with 20.2 percent and 3.8 percent of AH to AF-Like, respectively.In the second step, it was studied the physical and chemical properties of the humic acids produced: phenolic acidity, total acidity, the acidity of carboxyl groups, pH, CTC and gray, spectroscopy (FTIR, 13C NMR and ICP - OES), elemental analysis, thermal analysis (TGA) and structural analysis (SEM - EDS). There were some similarities with the AH s extracted from the soil with the difference being the degree of aromaticity which is very high (around 60 percent compared to 15 percent of the soil). Moreover, the relevant features were the CTC, which ranged 22 - 44 Cmolckg to the power of -1. This value is considered moderately high in relation to the approximate mean value of 25 Cmolckg to the power of -1 CTC , originated from Brazilian soil. The results obtained from FTIR spectroscopy and 13C NMR indicated that functionalization of the coal tailing (RJ), by any of the methods is relatively low (5.0 - 9.7 percent C-carboxylic acid) compared to AH from soil. Also showed similar structural and physical characteristics, as observed by scanning electron microscopy. In the third stage, a preliminary study on the retention capacity of the lead contained in synthetic (1000 ppm) solution by the AH obtained by the chemical processes method was performed. It was found an efficiency of 98 percent adsorption of the element when using a ratio of 1:1 (AH 1g : 1g Pb) and flow rate of 0.06 ml/min.

O lixiviado de aterro sanitário é uma água residuária com elevada concentração de DQO, DBO, amônia, traços de metais pesados e substâncias orgânicas dificilmente biodegradáveis, tais como substâncias húmicas e celulósicas (lignina). Dada essas características, torna-se necessário que ele seja recolhido e devidamente tratado para evitar danos ao meio ambiente e à saúde humana. Uma prática que tem sido adotada por alguns municípios brasileiros é o direcionamento do lixiviado para tratamento consorciado em estações de tratamento de esgoto (ETE). No entanto, são poucos os estudos que avaliam a eficácia desse procedimento. Um dos questionamentos sobre o tratamento biológico diz respeito à remoção do material orgânico dificilmente biodegradável, representado principalmente pelas substâncias húmicas e, dentro dessa classe, destaca-se a fração de ácidos húmicos no lixiviado. Nesse contexto, o presente trabalho teve como objetivo verificar a tratabilidade das soluções contendo lactose, lactose com ácidos húmicos, lactose com 2% em volume de lixiviado de aterro sanitário bruto e lactose com 2% em volume de lixiviado pré-tratado por \"air stripping\", quando submetidas ao tratamento biológico em reatores de lodos ativados em escala de bancada. Assim, buscou-se verificar se essa tecnologia de tratamento é capaz de estabilizar, ainda que parcialmente, compostos orgânicos de difícil biodegradação presentes no lixiviado. A quantificação das substâncias de difícil biodegradação antes e após o tratamento foi realizada pelo método tentativo do \"Equivalente em Ácidos Húmicos\" que se encontra em fase de estudo. Os resultados demonstraram que houve uma remoção parcial dessas substâncias. As análises de espectroscopia na região do infravermelho indicaram que não ocorreu a adsorção dos ácidos húmicos no lodo, o que pode ser uma evidencia de que a redução da concentração dessas substâncias é de fato devida ao seu consumo e não pela precipitação no lodo. Além disso, a adição de 2% em volume do lixiviado não ocasionou redução da população de microrganismos no sistema. / Leachate from sanitary landfills is a type of effluent with high concentrations of COD, BOD, ammonia, heavy metal traces and hardly biodegradable organic compounds such as humic and cellulosic substances (lignin). Thus this effluent needs to be collected and treated in order to prevent damages to the environment and to human health. A common practice in Brazilian cities is to destine the leachate to a sewage treatment plant (STP). However, there are few studies that assess the efficiency of this procedure. One of the questions regarding the biological treatment concerns its efficiency in removing hardly biodegradable organic compounds, represented in the most part by the humic substances, given the high levels of humic acid in the leachate. Within this context, the present study had the objective to verify the treatability of solutions containing lactose, lactose with humic acids, lactose with 2% (in volume) of untreated sanitary landfill leachate, and lactose with 2% of leachate pre-treated by air stripping, submitted to biological treatment in laboratory-scale activated sludge reactors. Thus this paper assessed if such treatment technology can stabilize, even if only partially, the hardly biodegradable organic compounds found in leachate. The quantification of these substances prior to and after treatment was made by using a tentative method called Humic Acids Equivalent, which is still in the phase of studies. The results show that there was a partial removal of these substances. The spectroscopy analyses on the infrared region indicated that there was no adsorption of humic acids onto the sludge, which evidences that the decrease in the levels of these substances was due to their consumption and not precipitation onto the sludge. Also, the addition of 2% of leachate did not reduce the population of microorganisms in the system.

Os solos têm um importante papel na maioria das atividades que ocorrem no planeta, dentre as quais, destaca-se a sua participação nos principais ciclos biogeoquímicos. A matéria orgânica do solo (MOS) tem um papel primordial na sustentabilidade ambiental, pois está relacionada com a ciclagem de carbono e nutrientes, sendo assim uma figura chave tanto para estudos relacionados com mudanças climáticas globais, quanto para estudos agronômicos. Um dos principais fluoróforos da MOS são as substâncias húmicas (SH), as quais são fracionadas de acordo com a sua solubilidade em ácidos húmicos (AH), ácidos fúlvicos (FA) e humina (HU). O estudo das propriedades ópticas da matéria orgânica é uma importante ferramenta para a compreensão estrutural e molecular das frações húmicas. Frente ao exposto, esse trabalho teve com objetivo estudar a gêneses de Espodossolos Amazônicos através da avaliação das características estruturais da matéria orgânica e suas propriedades de complexação com metais empregando diversas técnicas espectroscópicas. Os resultados mostraram grandes acúmulos de carbono em profundidade e que a Matéria Orgânica nesses Espodossolos Amazônico é constituída de quatro grupos: - mais recalcitrante, humificada e antiga; - lábil e jovem; - recalcitrante, pouco humificada e antiga; - humificada e jovem. Claramente o trabalho mostrou que o processo de humificação não tem relação direta com a datação do material orgânico, e que fatores como textura, presença de água e microorganismos influenciaram nos processos de formação e humificação desse material orgânico. Por fim, a fração AF do solo parece ter uma contribuição oriunda de lençóis freáticos, sua estrutura química varia pouco no perfil e possui seletividade na interação com os metais presentes nesses solos. Basicamente, o AF tem alta afinidade de complexação com Al. A fração AH, entretanto, mostrou-se menos seletiva, associando-se com vários tipos de metais, como K, Fe, Mg, Zn e Al; e sua estrutura química varia bastante no perfil do solo. Em função da diversidade de metais associados ao AH, ele deve ser o principal responsável pela fertilidade do solo. Desta forma, os resultados mostraram que as três frações húmicas estão envolvidas no processo de podzolização do solo, e que o AF tem papel predominante no transporte de Al e o AH é o responsável no transporte do Fe. / Soils play an important role in most of the activities that occur on the planet. It participation in the main biogeochemical cycles can be highlighted. Soil organic matter (SOM) plays a key role in environmental sustainability, since it is related to carbon and nutrient cycling, being essential for studies related to global climate change and agronomy. One of the major SOM fluorophore is the humic substances (HS), which is fractionated according to their solubility in humic acids (HA), fulvic acids (FA) and humin (HU). The study of the optical properties of the organic matter is an important tool for structural and molecular understanding of humic fractions. Based on that, this work aimed the study of the Amazonian Spodosols genesis through the evaluation of organic matter structural characteristics and its properties of metal complexation using different spectroscopic techniques. The main results of this research showed large carbon accumulations in depth. Furthermore, it was possible to infer how the Amazonian Spodosols organic matter is divided: - more recalcitrant, humified and old; - labile and young; - recalcitrant, little humified and old; - humified and young. The study demonstrated clearly that the humification process has no direct relationship with the organic material dating, and that factors such as texture, presence of water and microorganisms have influenced the formation and humification of that organic material. The FA fraction of the soil has a contribution from groundwater and its chemical structure varies little in depth. Additionally, FA showed selective interaction with soil metals. However, the HA fraction has been shown less selective, associate with various metal types, such as K, Fe, Mg, Zn and Al. Moreover, its chemical structure varies greatly in the soil depth. Due to the diversity of metals that the HA has affinity, it should be the main responsible of the soil fertility. After all, the results showed that all the three humic fractions are involved in the process of soil podzolization. Furthermore, the FA has a predominant role in Al transport as the HA is the responsable of Fe transport.

Radionuclides, 129I and 239,240Pu, are major products or by-products of nuclear fission and among the top risk drivers for waste disposal at the Savannah River Sites (SRS) and Rocky Flats Environmental Technology Sites (RFETS), respectively, due to their perceived mobility in the environment, excessive inventory, toxicity, and long half-life. The objective of this study is to investigate the role of natural organic matter in retarding or facilitating the migration of 129I and 239,240Pu in the Department of Energy (DOE) sites. Measurements of 127I and 129I in humic acids (HAs) and fulvic acids (FAs) obtained by five successive alkaline, two glycerol and one citric acid-alkaline extractions, demonstrated that these extractable humic substances (HS) together account for 54-56 percent and 46 percent of the total 127I and 129I in the soil, respectively. The variations among 127I and 129I concentrations, isotopic ratios (129I/127I), chemical properties of all these humic substances indicated iodine was bound to a small-size aromatic subunit (~10 kDa), while the large-size subunit (~90 kDa), which likely linked the small-size unit through some weak chemical forces, determined the relative mobility of iodine bound to organic matter. Soil resuspension experiments simulating surface runoff or stormflow and erosion events were conducted with soils collected from SRS. Results showed that 72-77 percent of the newly-introduced I- or IO3- were irreversibly sequestered into the organic-rich soil, while the rest was transformed into colloidal and dissolved organo-iodine by the soil. The resulting iodine remobilization contradicts the conventional view that considers only I- or IO3- as the mobile forms. Quantitative structure analysis by 13C DPMAS NMR and solution state 1H NMR on these humic substances indicate that iodine is closely related to the aromatic regions containing esterified products of phenolic and fomic acid or other aliphatic carboxylic acids, amide functionalities, quinone-like structure activated by electron-donating groups (e.g., NH2) or hemicelluloses-lignin-like complex with phenyl-glycosidic linkage. The micro-molecular environment, such as the hydrophobic aliphatic periphery hindering the active aromatic cores and the hydrophilic polysaccharides favoring its accessibility towards hydrophilic iodine species, play another key role in the interactions between iodine and SOM. NMR spectra of the colloidal organic Pu carrier which can potentially be released from the soil during the surface runoff or stormflow showed Pu was transported, at sub-pM concentrations, by a cutin-derived soil degradation products containing siderophore-like moieties and virtually all mobile Pu.

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.