Corantes orgânicos são uma importante classe de poluentes ambientais, sendo que a natureza da interação de tais espécies com ácidos húmicos determina seu comportamento e destino ambiental. Este trabalho investiga abordagens diferentes para a síntese de nanopartículas de ouro-ácido húmico (NPs Au/AH), o desempenho destas partículas como sensores para a determinação de traço de corantes orgânicos e da natureza da sua interação química com ácidos húmicos por técnicas de espectroscopia Raman intensificada por superfície (surface-enhanced Raman scattering, SERS). As nanopartículas de ouro foram obtidas de forma direta em meio aquoso. A síntese foi realizada na presença de ácido húmico em vários valores de pH e na presença e na ausência de citrato de sódio. Nesta abordagem, o ácido húmico apresenta propósitos diferentes. Na síntese das nanopartículas, ele serve como agente redutor e para a estabilização da superfície, impedindo a coalescência das nanopartículas em meio aquoso. Considerando-se a utilização de nanopartículas como substratos SERS-ativos, o ácido húmico serve como uma fase de extração associada com a plataforma SERS, favorecendo a interação dos corantes orgânicos com as nanopartículas metálicas. Esta abordagem pode ser utilizada para aumentar a sensibilidade e seletividade da técnica SERS e evitar a interferência de outras espécies em solução. É também importante mencionar que o ácido húmico dá origem a um espectro Raman muito fraco e, portanto, não interfere de forma significativa na detecção espectroscópica das espécies de interesse. As NPs Au/AH obtidas foram caracterizadas por espectroscopia eletrônica, microscopia eletrônica de varredura e SERS, a fim de estabelecer uma correlação entre a sua morfologia, plasmon superficial, e seu uso potencial como substratos SERS. As NPs Au/AH foram utilizadas como substratos SERS no estudo de corantes têxteis aniônicos e catiônicos. Os espectros Raman, nestes casos, foram atribuídos ao complexo formado pelo ácido húmico e cada uma das espécies de interesse. Os resultados obtidos revelaram uma dependência significativa entre as propriedades morfológicas e eletrônicas das NPs Au/AH com o procedimento de síntese, e também uma interação preferencial entre as nanopartículas e os corantes catiônicos. Conclui-se que as NPs Au/AH podem proporcionar uma abordagem útil para a caracterização espectroscópica de espécies relevantes para o ambiente e sua interação química com os ácidos húmicos, através do uso da espectroscopia Raman intensificada pela superfície / Organic dyes are an important class on environmental pollutants, and the nature of the interaction of such species with humic acid strongly determines their environmental behavior and fate. This work investigates different approaches for the synthesis of humic acid-gold nanoparticles (HA-AuNP), the performance of these particles as sensors for trace determination of organic dyes and the nature of their chemical interaction with humic acids by surface-enhanced Raman scattering (SERS). The Au nanoparticles were obtained by direct fabrication in aqueous media.The synthesis were carried out in the presence of humic acid at various pH values, and in the presence and absence of sodium citrate. In this approach, humic acid serves different purposes. In the synthesis of the nanoparticles, they serve as reducing agent and for surface stabilization, preventing coalescence of the nanoparticles in aqueous media. Considering the use of the nanoparticles as SERSactive substrates, the humic acid serves as an extraction phase associated with the SERS platform, favoring the interaction of the organic dyes with the metallic nanoparticles. This approach can be used to enhance the sensitivity and selectivity of SERS technique and avoid interference from other species in solution. It is also important to mention that the humic acid gives rise to a very weak Raman spectrum, and therefore does not interfere significantly in the spectroscopic detection of the species of interest. The obtained HA-AuNPs were characterized by electronic spectroscopy, scanning electron microscopy and SERS, in order to establish a correlation between their morphology, surface plasmon, and their potential use as SERS platforms. The HA-AuNPs have been applied as SERS substrates for anionic and cationic textile dyes. The recorded Raman spectra are, in these cases, assigned to the complex formed by the humic acid and each of the species of interest. The obtained results revealed a significant dependence on the morphological and electronic properties of the HA-AuNPs with the synthesis procedure, and also a strong interaction between the nanoparticles and cationic dies. We conclude that HA-AuNP may provide a valuable approach for the spectroscopic characterization of environmentally relevant species and their chemical interaction with humic acids, through the use of surface enhanced Raman spectroscopy

A Amazônia representa a maior biodiversidade do mundo e representa um reservatório enorme e dinâmico de carbono, não só na biomassa, mas também no solo. O ciclo do carbono neste bioma é muito importante, principalmente para questões abordadas às mudanças climáticas. Avaliar e compreender a dinâmica do carbono e outros elementos no solo da Amazônia pode ajudar os cientistas a melhorar os modelos e antecipar cenários. Novos métodos, que permitem medições de carbono do solo in situ, são uma abordagem fundamental para este tipo de região, devido aos custos financeiros para a coleta e envio de amostras de solo da floresta para o laboratório, e demanda muito tempo nesta atividade. No presente estudo, uma topossequência de um sistema Latossolo-Espodossolo com caulim associado, desenvolvido a partir de rochas granito gnáissicas do embasamento cristalino, foi estudada. As amostras foram coletadas em São Gabriel da Cachoeira, estado do Amazonas. Dois perfis de solo: Espodossolo Humilúvico (P1) no topo e Latossolo Amarelo (P2) na meia encosta da topossequência foram descritos e amostrados em um total de dezoito amostras. Os objetivos principais foram avaliar e caracterizar através de métodos químicos e espectroscópicos a matéria orgânica e a composição elementar nestes solos arenosos utilizando a análise elementar (CHNS), espectroscopia de emissão ótica com plasma induzido por laser (LIBS), espectrometria de emissão ótica com plasma acoplado indutivamente (ICP OES), espectroscopia de fluorescência induzida por laser (FIL), fluorescência de luz UVVisível e absorção de radiação na região no UV-Visível. Através dos resultados obtidos pela análise elementar foi possível notar que para o Espodossolo Humilúvico houve variações diferenciadas nos teores de carbono, mas para o Latossolo Amarelo, não se pode inferir uma tendência de incremento ou decréscimo do teor de carbono ao longo do perfil, pois o teor de carbono para a maioria das amostras de solo foi inferior a 0,3%, o limite de detecção do CHNS. A espectroscopia de matrizes de fluorescência de excitação-emissão (MEE) foi uma técnica mais seletiva e sensível do que a fluorescência bidimensional para os ácidos húmicos (AH), mostrando informações interessantes, variações estruturais e grande diferença entre os cromóforos que emitem fluorescência nos extratos de ácido fúlvico 2 (EAF2) e AH. A combinação dos espectros de MEE com a análise de fatores paralelos (PARAFAC) permitiu caracterizar qualitativamente os EAF2, podendo identificar e associar com mais clareza os três fluoróforos obtidos, com seus respectivos componentes, ácidos fúlvicos (grupos de fluoróforos simples e complexos) e proteína, com diagnóstico de consistência do tensor núcleo (CORCONDIA) de 85,8%. Esta combinação permitiu caracterizar quantitativamente os AH, identificando a contribuição das intensidades de dois fluoróforos, associados aos AH, grupos de fluoróforos mais complexos e simples, com CORCONDIA de 84,2%. A partir dos resultados de LIBS, uma forte correlação foi encontrada e os coeficientes de correlação de Pearson\'s obtidos para o ajuste logarítmico foi de R = 0,98 e R = 0,99 para o carbono e o alumínio, respectivamente, entre os valores obtidos por LIBS e as técnicas de referências (CHNS e ICP OES) para o Espodossolo Humilúvico. Nenhuma relação foi observada para o ferro, provavelmente devido aos teores estarem abaixo do limite de detecção. A técnica FIL mostrou para o Espodossolo Humilúvico que o horizonte de transição (Tr) estaria funcionando como uma \"peneira molecular\", acumulando a matéria orgânica pouco humificada, permitindo a passagem para os horizontes de caulim (K1 e K2) de compostos com estruturas mais humificadas, mais complexas, de difícil degradação (mais recalcitrantes), mas de menor tamanho molecular, como anéis aromáticos condensados e/ou conjugação de anéis aromáticos simples, corroborando com a eficiência da extração do AH. Para o Latossolo Amarelo, observou-se um aumento no grau de humificação do horizonte superficial BA em relação ao A2. Logo, estes resultados contribuem para um melhor entendimento sobre a quantificação de carbono, grau de humificação e alterações estruturais da matéria orgânica dos solos arenosos da região de São Gabriel da Cachoeira na Amazônia. / The Amazon represents the world\'s biggest biodiversity, comprehending a large and dynamic carbon pool, considering its biomass and soil, as well. The carbon cycle in this biome is very important, especially in questions regarding climatic changes. To evaluate and to understand the carbon and other elements cycles in Amazonian soil can help scientists to improve models and foresee scenarios. New methods, allowing carbon measurements on site, are a crucial approach for this kind of region, due to the financial costs to collect and ship soil samples from forest to laboratory, and the time spent in this activity. In the present study, it was analyzed a topsequence of an Oxisol-Spodosol system with kaolin associated, generated from granitic-gneiss rocks of crystalline basement. The soil samples were collected in São Gabriel da Cachoeira, Amazonas state, Brazil, considering two different soil profiles: Spodosols (P1), at the top layer, and yellow Oxisols (P2) at the topsequence hillside, representing a total of eighteen samples. The main purpose of this study was to evaluate and characterize the organic matter content and elemental composition by chemical and spectroscopic methods using elemental analysis (CHNS), laserinduced breakdown spectroscopy (LIBS), inductively coupled plasma optical emission spectrometry (ICP OES), laser-induced fluorescence spectroscopy (LIFS), fluorescence spectroscopy and UV-Visible spectroscopy. The CHNS results showed differences in the carbon content for the Spodosol (P1) samples; however, it was not observed any differences for the Oxisol (P2) samples, once the carbon content data obtained for these samples were lower than the equipment detection limit (0.3%). The excitation-emission matrix (EEM) fluorescence spectroscopy was more sensitive for detecting humic acids (HA) than the two-dimensional fluorescence spectroscopy, showing interesting information, structural variations and large difference among chromophores that emit fluorescence in fulvic acid extracts 2 (EAF2) and HA. The EAF2 were qualitatively characterized by combining the EEM spectra with parallel factor analysis (PARAFAC), which allowed to identify clearly the three fluorophores obtained and their respective components, fulvic acids (simple and complex groups of fluorophores) and protein, with core consistency diagnostic (CORCONDIA) of 85.8%. These data also allowed to quantify the HA, identifying contributions of intensities from two fluorophores associated with HA, complex groups and simple fluorophores, presenting CORCONDIA of 84.2%. Regarding the carbon and aluminum content results for the Spodosol samples, a strong correlation was found between the LIBS values and the standard techniques (CHNS and ICP OES). The Pearson\'s coefficients obtained by logarithmic fit were R = 0.98 and R = 0.99 for carbon and aluminum, respectively. It was not observed any differences for the iron contents from the analyzed samples, probably due to the low content observed regarding the detection limit this element presents. The LIFS technique indicated that the transition horizon (Tr) would be acting as a \"molecular sieve\" in the Spodosol soil (P1), accumulating less humified organic matter, and allowing passage to kaolin horizons (K1 and K2) of compounds with more humified, more complex, difficult to degrade (recalcitrant) structures, but with lower molecular size, such as condensed aromatic rings and/or combination of simple aromatic rings. These results were in accordance to the HA extraction efficiency. For the yellow Oxisol (P2) samples, it was observed a humification degree increase in the surface horizon BA compared to the A2 horizon. This way, the data obtained contribute to a better understanding regarding carbon quantification, humification degree and organic matter structural alterations on sandy soils in São Gabriel da Cachoeira, at the Amazonian region.

A Amazônia representa a maior biodiversidade do mundo e representa um reservatório enorme e dinâmico de carbono, não só na biomassa, mas também no solo. O ciclo do carbono neste bioma é muito importante, principalmente para questões abordadas às mudanças climáticas. Avaliar e compreender a dinâmica do carbono e outros elementos no solo da Amazônia pode ajudar os cientistas a melhorar os modelos e antecipar cenários. Novos métodos, que permitem medições de carbono do solo in situ, são uma abordagem fundamental para este tipo de região, devido aos custos financeiros para a coleta e envio de amostras de solo da floresta para o laboratório, e demanda muito tempo nesta atividade. No presente estudo, uma topossequência de um sistema Latossolo-Espodossolo com caulim associado, desenvolvido a partir de rochas granito gnáissicas do embasamento cristalino, foi estudada. As amostras foram coletadas em São Gabriel da Cachoeira, estado do Amazonas. Dois perfis de solo: Espodossolo Humilúvico (P1) no topo e Latossolo Amarelo (P2) na meia encosta da topossequência foram descritos e amostrados em um total de dezoito amostras. Os objetivos principais foram avaliar e caracterizar através de métodos químicos e espectroscópicos a matéria orgânica e a composição elementar nestes solos arenosos utilizando a análise elementar (CHNS), espectroscopia de emissão ótica com plasma induzido por laser (LIBS), espectrometria de emissão ótica com plasma acoplado indutivamente (ICP OES), espectroscopia de fluorescência induzida por laser (FIL), fluorescência de luz UVVisível e absorção de radiação na região no UV-Visível. Através dos resultados obtidos pela análise elementar foi possível notar que para o Espodossolo Humilúvico houve variações diferenciadas nos teores de carbono, mas para o Latossolo Amarelo, não se pode inferir uma tendência de incremento ou decréscimo do teor de carbono ao longo do perfil, pois o teor de carbono para a maioria das amostras de solo foi inferior a 0,3%, o limite de detecção do CHNS. A espectroscopia de matrizes de fluorescência de excitação-emissão (MEE) foi uma técnica mais seletiva e sensível do que a fluorescência bidimensional para os ácidos húmicos (AH), mostrando informações interessantes, variações estruturais e grande diferença entre os cromóforos que emitem fluorescência nos extratos de ácido fúlvico 2 (EAF2) e AH. A combinação dos espectros de MEE com a análise de fatores paralelos (PARAFAC) permitiu caracterizar qualitativamente os EAF2, podendo identificar e associar com mais clareza os três fluoróforos obtidos, com seus respectivos componentes, ácidos fúlvicos (grupos de fluoróforos simples e complexos) e proteína, com diagnóstico de consistência do tensor núcleo (CORCONDIA) de 85,8%. Esta combinação permitiu caracterizar quantitativamente os AH, identificando a contribuição das intensidades de dois fluoróforos, associados aos AH, grupos de fluoróforos mais complexos e simples, com CORCONDIA de 84,2%. A partir dos resultados de LIBS, uma forte correlação foi encontrada e os coeficientes de correlação de Pearson\'s obtidos para o ajuste logarítmico foi de R = 0,98 e R = 0,99 para o carbono e o alumínio, respectivamente, entre os valores obtidos por LIBS e as técnicas de referências (CHNS e ICP OES) para o Espodossolo Humilúvico. Nenhuma relação foi observada para o ferro, provavelmente devido aos teores estarem abaixo do limite de detecção. A técnica FIL mostrou para o Espodossolo Humilúvico que o horizonte de transição (Tr) estaria funcionando como uma \"peneira molecular\", acumulando a matéria orgânica pouco humificada, permitindo a passagem para os horizontes de caulim (K1 e K2) de compostos com estruturas mais humificadas, mais complexas, de difícil degradação (mais recalcitrantes), mas de menor tamanho molecular, como anéis aromáticos condensados e/ou conjugação de anéis aromáticos simples, corroborando com a eficiência da extração do AH. Para o Latossolo Amarelo, observou-se um aumento no grau de humificação do horizonte superficial BA em relação ao A2. Logo, estes resultados contribuem para um melhor entendimento sobre a quantificação de carbono, grau de humificação e alterações estruturais da matéria orgânica dos solos arenosos da região de São Gabriel da Cachoeira na Amazônia. / The Amazon represents the world\'s biggest biodiversity, comprehending a large and dynamic carbon pool, considering its biomass and soil, as well. The carbon cycle in this biome is very important, especially in questions regarding climatic changes. To evaluate and to understand the carbon and other elements cycles in Amazonian soil can help scientists to improve models and foresee scenarios. New methods, allowing carbon measurements on site, are a crucial approach for this kind of region, due to the financial costs to collect and ship soil samples from forest to laboratory, and the time spent in this activity. In the present study, it was analyzed a topsequence of an Oxisol-Spodosol system with kaolin associated, generated from granitic-gneiss rocks of crystalline basement. The soil samples were collected in São Gabriel da Cachoeira, Amazonas state, Brazil, considering two different soil profiles: Spodosols (P1), at the top layer, and yellow Oxisols (P2) at the topsequence hillside, representing a total of eighteen samples. The main purpose of this study was to evaluate and characterize the organic matter content and elemental composition by chemical and spectroscopic methods using elemental analysis (CHNS), laserinduced breakdown spectroscopy (LIBS), inductively coupled plasma optical emission spectrometry (ICP OES), laser-induced fluorescence spectroscopy (LIFS), fluorescence spectroscopy and UV-Visible spectroscopy. The CHNS results showed differences in the carbon content for the Spodosol (P1) samples; however, it was not observed any differences for the Oxisol (P2) samples, once the carbon content data obtained for these samples were lower than the equipment detection limit (0.3%). The excitation-emission matrix (EEM) fluorescence spectroscopy was more sensitive for detecting humic acids (HA) than the two-dimensional fluorescence spectroscopy, showing interesting information, structural variations and large difference among chromophores that emit fluorescence in fulvic acid extracts 2 (EAF2) and HA. The EAF2 were qualitatively characterized by combining the EEM spectra with parallel factor analysis (PARAFAC), which allowed to identify clearly the three fluorophores obtained and their respective components, fulvic acids (simple and complex groups of fluorophores) and protein, with core consistency diagnostic (CORCONDIA) of 85.8%. These data also allowed to quantify the HA, identifying contributions of intensities from two fluorophores associated with HA, complex groups and simple fluorophores, presenting CORCONDIA of 84.2%. Regarding the carbon and aluminum content results for the Spodosol samples, a strong correlation was found between the LIBS values and the standard techniques (CHNS and ICP OES). The Pearson\'s coefficients obtained by logarithmic fit were R = 0.98 and R = 0.99 for carbon and aluminum, respectively. It was not observed any differences for the iron contents from the analyzed samples, probably due to the low content observed regarding the detection limit this element presents. The LIFS technique indicated that the transition horizon (Tr) would be acting as a \"molecular sieve\" in the Spodosol soil (P1), accumulating less humified organic matter, and allowing passage to kaolin horizons (K1 and K2) of compounds with more humified, more complex, difficult to degrade (recalcitrant) structures, but with lower molecular size, such as condensed aromatic rings and/or combination of simple aromatic rings. These results were in accordance to the HA extraction efficiency. For the yellow Oxisol (P2) samples, it was observed a humification degree increase in the surface horizon BA compared to the A2 horizon. This way, the data obtained contribute to a better understanding regarding carbon quantification, humification degree and organic matter structural alterations on sandy soils in São Gabriel da Cachoeira, at the Amazonian region.

A destinação dos resíduos sólidos constitui um sério problema ambiental para a humanidade. Por meio do processo de vermicompostagem, pode-se obter a reciclagem dos resíduos orgânicos, resultando em um material mais humificado, de grande potencial agrícola e de sequestro de carbono atmosférico quando aplicado ao solo. Para que se tenha segurança agronômica quando da utilização de resíduos é necessário que se conheçam os mecanismos de incorporação, mineralização e liberação de nutrientes, ou seja, a dinâmica da matéria orgânica no solo. Dessa forma, contribui-se para a manutenção do ciclo da matéria orgânica (devolvendo ao solo parte da matéria orgânica que lhe é tirada), e também para uma destinação ambientalmente adequada de resíduos orgânicos. Esta é a orientação geral deste estudo. Compilando os resultados obtidos por métodos convencionais e técnicas espectroscópicas para caracterização das amostras coletadas durante a vermicompostagem dos ácidos húmicos extraídos, foi possível fazer o monitoramento contínuo do processo de degradação de diferentes resíduos orgânicos (bagaço de laranja, torta de filtro e esterco bovino). Para execução dos experimentos foram montadas 9 pilhas (P) de compostagem de bagaço de laranja + esterco bovino, torta de filtro + esterco bovino e esterco bovino (100%). Após a estabilização da temperatura os compostos foram tranferidos aos vermicompostores. O monitoramento foi realizado por 135 dias com medidas diárias de temperatura, controle semanal de umidade e coletas quinzenais das amostras para caracterização química e extração de ácidos húmicos. Observaram-se três fases de temperatura durante a primeira etapa da vermicompostagem (compostagem). Primeira fase: mesofílica, em que houve um aumento na temperatura, a qual alcançou valores superiores a 30 °C; segunda fase: termofílica, em que a temperatura atingiu valores máximos, superiores a 60 °C para as pilhas P1, P2 e P3 (bagaço de laranja + esterco bovino), as quais apresentaram as temperaturas mais altas dentre os tratamentos; terceira fase: esfriamento e maturação. Foi possível acompanhar a dinâmica do processo de vermicompostagem química e espectroscopicamente. A caracterização química dos vermicompostos (teor de C e N, C/N, pH, CTC, macro e micronutrientes) está de acordo com o que é exigido pela Instrução Normativa no 25, do Ministério de Agricultura, Pecuária e Abastecimento. Estas análises evidenciaram o potencial fertilizante dos vermicompostos produzidos. A análise das características estruturais dos ácidos húmicos revelou diferenças entre os ácidos húmicos estudados. Os espectros de FTIR referentes a todos os tratamentos apresentaram bandas típicas de substâncias húmicas indicando algumas transformações a nível molecular como a perda de estruturas mais lábeis devido ao processo de biodegração. A presença de sistemas aromáticos foi observada por meio da técnica de UV-Vis, principalmente por meio das baixas razões E2/E4, o que é indicativo da presença de estruturas porfirínicas relacionadas à lignina. Assim como os resultados apresentados por FTIR os espectros de RMN de 13C apresentam picos correspondentes à degradação de carboidratos. Houve aumento do teor de aromaticidade e diminuição do teor de alifaticidade dos AH com o tempo de vermicompostagem, exceto para os referentes ao tratamento com torta de filtro que apresentou comportamento contrário. Em geral o desenvolvimento das plantas que receberam adubação orgânica foi similar ao desenvolvimento das plantas que receberam adubação mineral comercialmente recomendada e significativamente superior ao das plantas referente ao tratamento testemunha. Para o vertissolo o efeito dos vermicompostos sobre os atributos altura e biomassa das plantas foi mascarado, possivelmente pelo alto teor de matéria orgânica naturalmente existente naquele solo. A análise cromatográfica do óleo essencial extraído do Manjericão mostrou que a adubação orgânica influenciou positivamente a produção do principal componente do óleo essencial, o linalol, havendo aumento de seu teor com o aumento da dosagem de vermicomposto aplicado, nos dois solos estudados. Dos tratamentos analisados, o referente à adubação com vermicomposto de torta de filtro + esterco bovino 30 t ha-1, em vertissolo, apresentou o maior teor de linalol (34,90 %). De modo geral constata-se a viabilidade do uso de vermicompostos de misturas de bagaço de laranja e torta de filtro com esterco bovino como alternativa ao uso de fertilizantes minerais, contudo o manejo e as implicações na nutrição de plantas e a plena produtividade das culturas ainda representa desafio importante para as pesquisas. Dentre as doses dos vermicompostos avaliadas, em geral a aplicação da dosagem intermediária (30 t ha-1 ou 3,0%) apresenta resultados superiores em termos de qualidade nutricional e da MOS, sendo dessa forma a melhor opção para manejo do solo para cultivo de Manjericão. Em estudos futuros, a dosagem 30 t ha-1 poderia ser adotada como dosagem agronômica recomendada, bem como a mistura de resíduos orgânicos agroindustriais para produção do vermicomposto. / The disposal of solid waste is a serious environmental problem for humanity. By means of the vermicomposting process, one can get the recycling of organic waste, resulting in a humified material of great agricultural potential and atmospheric carbon sequestration when applied to soil. To have agronomic security when using waste is necessary to know the mechanisms of incorporation, mineralization and release of nutrients, or the dynamics of soil organic matter. Thus, it contributes to maintaining the organic matter cycle (returning to the ground of the organic matter that is taken away), and for an environmentally proper disposal of organic waste. This is the general direction of this study. Compiling the results obtained by conventional methods and spectroscopic techniques for characterization of samples collected during vermicomposting of extracted humic acids, it was possible the continuous monitoring of the degradation process of different organic waste (orange bagasse, filter cake and manure). For execution of the experiments were set 9 cells (P) composting orange peel + cattle manure, filter cake + cattle manure and manure. After temperature stabilization compounds were tranferidos to vermicompostores. The monitoring was held for 135 days with daily measurements of temperature, humidity and weekly control fortnightly collections of samples for chemical and extraction of humic acids. They observed three stages of temperature for the first stage of vermicomposting (composting). First stage: mesophilic, wherein an increase in temperature, which reached values higher than 30° C; second phase: Thermophilic, wherein the maximum temperature reached values higher than 60° C for stacks P1, P2 and P3 (orange peel + cattle manure), which had the highest temperature among treatments; third phase: cooling and maturation. It was possible to follow the dynamics of the process of chemical and spectroscopically vermicomposting. The chemical characterization of vermicompost (C and N content, C/N, pH, CEC, macro and micronutrients) is in line with what is required by the Normative Instruction 25, the Ministry of Agriculture, Livestock and Supply. These analyzes showed the fertilizer potential of the vermicomposts. The analysis of the structural characteristics of humic acids showed differences between the studied humic acids. FTIR spectra for all of the treatments showed typical bands of humic substances indicating some changes at the molecular level as the loss of more labile structures due to the biodegradation process. The presence of aromatic systems was observed by UV-Vis technique mainly through the lower ratios E2/E4, which is indicative of the presence of porfirínicas structures related to lignin. As the results presented by FTIR the 13C NMR spectra show peaks corresponding to the degradation of carbohydrates. There was an increase of aromaticity content and decreased alifaticidade content of AH with a time of vermicomposting, except for those related to treatment with filter cake which showed opposite behavior. In general the development of the plants that received organic fertilization was similar to the development of the plants that received commercially recommended mineral fertilization and significantly higher than the plants referring to the control treatment. For the vertisol the effect of the vermicompost on the height and biomass attributes of the plants was masked, possibly due to the high content of organic matter naturally present in that soil. The chromatographic analysis of the essential oil extracted from Manjericão showed that the organic fertilization positively influenced the production of the main component of the essential oil, linalol, increasing its content with the increase of the applied vermicompost dosage, in the two studied soils. Of the analyzed treatments, the one referring to the fertilization with vermicompost of filter cake + bovine manure 30 t ha-1, in vertisol, presented the highest content of linalool (34.90%). In general, it is possible to verify the viability of the use of vermicompostos of mixtures of orange bagasse and filter cake with bovine manure as an alternative to the use of mineral fertilizers, however the management and the implications in plant nutrition and the full productivity of the crops still represents an important research challenge. Among the doses of vermicompost evaluated, in general the application of the intermediate dosage (30 t ha-1 or 3.0%) presents superior results in terms of nutritional quality and MOS, being thus the best option for soil management for cultivation Of Basil. In future studies, the 30 t ha-1 dosage could be adopted as the recommended agronomic dosage, as well as the mixture of agroindustrial organic residues for vermicompost production.

Submitted by Leticia Schettini (leticia@ufrrj.br) on 2016-09-21T15:12:59Z No. of bitstreams: 1 2011 - Camila Pinheiro Nobre.pdf: 2714138 bytes, checksum: bc436d879ddfded703d4d5fea9f9943c (MD5) / Made available in DSpace on 2016-09-21T15:12:59Z (GMT). No. of bitstreams: 1 2011 - Camila Pinheiro Nobre.pdf: 2714138 bytes, checksum: bc436d879ddfded703d4d5fea9f9943c (MD5) Previous issue date: 2011-02-17 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior-CAPES / The aim of this study was to observe the germination, production of glomalin and monitor development of species of mycorrhizal fungi (AMF) of the germplasm bank of Embrapa in root organ culture (ROC) of basil and bryophytes in vitro, analyzing their interaction with the hosts and the influence of the culture medium enriched with humic acids on fungal growth and bryophyte Lunularia cruciata. For this, some AMF species were selected and had their glomerospores extracted and subjected to surface disinfection process, placed in water-agar medium and temperature-controlled chamber to germinate. A germination test was conducted for 15 days, and the results were analyzed by ANOVA and Tukey test applied to 5% probability. Species with germinated glomerospores (Gigaspora margarita, Glomus manihots, Scutellospora heterogama and Glomus proliferum) were placed in ROC of purple basil where they had their growth observed until 100 days after inoculation. Also as part of the characterization of AMF species it was quantified the level of glomalin in the samples of multiplication and the results were subjected to analysis of variance and Scott-Knott test at 5% probability. In the second chapter it was investigated the effect of mycorrhizal association in ROC of purple basil, and in the third chapter the influence of different concentrations of humic acid and association with growth of Lunularia cruciata (area and length). The results were submitted to ANOVA and Tukey test at 5% probability. Scutellospora heterogama was the species with higher germination rates of glomerosporos, followed by Gigaspora margarita. The species of Glomus sporulated after formation of symbiosis. The amount of glomalin produced by different AMF was distinct, especially in total glomalin fraction. Different AMF species did not show difference in efficiency to promote development of Ocimum basilicum transformed roots. The growth of basil transformed roots in the MSR was extended from 15 days after inoculation with mycorrhizal fungi. The usage of humic acids in the culture medium in concentrations of 20 and 80 mg CL-1 enhanced growth of bryophyte L. cruciata, and its association with mycorrhizal fungi, as well as promoted the highest number of spores of Gl. proliferum. The association L. cruciata and AMF was characterized as mutualistic, since both had advantages in growth and sporulation. Gigaspora margarita and Glomus proliferum increased growth of Lunularia cruciata. / O objetivo do trabalho foi observar a germina??o e produ??o de glomalina e acompanhar desenvolvimento de esp?cies de fungos micorr?zicos arbusculares (FMA) do banco de germoplasma da Embrapa em ra?zes geneticamente modificadas de manjeric?o e em bri?fitas in vitro. Ainda, avaliar sua intera??o com os hospedeiros e a influ?ncia de meio de cultura enriquecido com ?cidos h?micos no crescimento do fungo e da bri?fita Lunularia cruciata. Para isso algumas esp?cies de FMAs foram selecionadas e tiveram seus glomerosporos extra?dos e submetidos ao processo de desinfesta??o superficial, colocados em meio Agar?gua e c?mara com temperatura controlada para germinar. Realizou-se teste de germina??o por 15 dias e os resultados foram submetidos a an?lise de vari?ncia e aplicado teste de Tukey ? 5% de probabilidade. Esp?cies com glomerosporos germinados (Gigaspora margarita, Glomus manihots, Scutellospora heterogama e Glomus proliferum) foram colocadas em ra?zes modificadas de manjeric?o roxo onde tiveram seu crescimento observado at? 100 dias ap?s a inocula??o. Ainda como parte da caracteriza??o de esp?cies de FMAs foi realizado a quantifica??o dos teores de glomalina nas amostras de multiplica??o sendo os resultados submetidos a an?lise de vari?ncia e aplicado teste de Scott-Knott ? 5% de probabilidade. No segundo cap?tulo foi verificado o efeito da associa??o FMAs em ra?zes modificadas de manjeric?o roxo e no terceiro cap?tulo a influ?ncia da associa??o ?cido h?mico em diferentes concentra??es, bri?fita Lunularia cruciata (?rea e comprimento) e FMAs. Os resultados foram submetidos ? an?lise de vari?ncia e teste de Tukey a 5% de probabilidade. Scutellospora heterogama foi a esp?cie com maiores taxas de germina??o de glomerosporos, seguida da Gigaspora margarita. As esp?cies de Glomus esporularam logo ap?s a forma??o da simbiose. A quantidade de glomalina produzida pelos diferentes FMAs foi distinta, em especial na fra??o glomalina total. As diferentes esp?cies de FMAs n?o apresentaram distin??o na efici?ncia de promover o desenvolvimento das ra?zes transformadas de Ocimum basilicum. O crescimento de ra?zes transformadas de manjeric?o em meio MSR foi ampliado a partir dos 15 dias ap?s a inocula??o de fungos micorr?zicos. O uso de ?cidos h?micos no meio de cultura em concentra??es de 20 e 80 mg C.L-1 incrementou o crescimento da bri?fita Lunularia cruciata e sua associa??o com fungos micorr?zicos arbusculares, assim como promoveram a maior esporula??o de Gl. proliferum. A associa??o Lunularia cruciata e FMAs foi caracterizada como mutualista j? que ambos apresentaram benef?cios em crescimento e esporula??o. Gigaspora margarita e Glomus proliferum promoveram maior crescimento de Lunularia cruciata.

Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2017-02-07T18:57:15Z No. of bitstreams: 1 2016 - Shirlei Almeida Assun??o.pdf: 1407109 bytes, checksum: 346922df83ba0b7c92b59002d73737df (MD5) / Made available in DSpace on 2017-02-07T18:57:15Z (GMT). No. of bitstreams: 1 2016 - Shirlei Almeida Assun??o.pdf: 1407109 bytes, checksum: 346922df83ba0b7c92b59002d73737df (MD5) Previous issue date: 2016-02-22 / CAPES / Faperj / Brazil is the biggest sugarcane producer of the world with cultivated area superior to nine millions hectares. To reach economically viable productivity levels it is necessary to make use of high amounts of N fertilizers. These fertilizers are high cost and they also can contribute to emission of greenhouse gases and pollution of watercourses, as well as, to influence directly on the decomposition of the soil organic matter (SOM). In this context to understand how interactions between nitrogen and SOM occurs in sugarcane fields is important from both economic and environmental points of view. Therefore, the objective of this study was to evaluate quantity and quality of soil carbon when different doses of nitrogen are added in the form of ammonium sulphate in a sugarcane raw agro-ecosystem in an ultisol from Coastal Plains. The experiment was conduced in sugarcane fields renovated in 2009 in area of the company LASA alcohol distillery, in Linhares - ES, in an Ultisol with sandy to medium texture, from Coastal Plain environment. The variety of sugarcane (Saccharum spp.) used was RB918639. There were evaluated five treatments of N ammonium sulphate doses: 0 (control), 80, 100, 120 and 160 kg of N per ha-1 with four repetitions, established under experimental design of randomized blocks. Each experimental unit (plot) was 70 m? (5 lines with 10 m, spaced by 1.4 m between lines). Samples of plant and soil were collected in September 2013 and 2014, corresponding to 4th and 5th harvest. The results indicated that among the N doses evaluated, the doses of 100 and 120 kg were the most efficient on accumulating carbon on the humic fractions, particle size, densimetric and oxidizable carbon fractions. The dose of 160 kg was the less effective to carbon accumulation on the humic fractions, particle size, densimetric and oxidizable carbon fractions. Total nitrogen, natural abundance of 13C and 15N, stem and straw production were not influenced by N rates, with no differences on any of the seasons. About the elemental composition of humic acids (HA), the quantities of chemicals were very similar between doses and coherent with results in the literature for the HA. In the E4/E6 ratio, the dose of 160 kg of N was the one with the lowest E4/E6 ratio. Regarding the infrared with Fourier transformation it was observed the predominance of aliphatic groups, and the analysis of major components enabled the clear separation of the effects from different N doses. In the 13CNMR prevailed larger amounts of aliphatic carbons, it was confirmed with the aliphaticity index of the samples, the results were above 80% for all samples. It was also verified through the 13 CNMR that the control area and the dose of 160 kg had the lowest aromaticity rates. Therefore, it was concluded that different fractionations of organic matter along with spectroscopic techniques were effective on evaluating the influence of different nitrogen doses to the decomposition of SOM. / O Brasil ? o maior produtor mundial de cana-de-a??car, com ?rea plantada que ultrapassa os nove milhoes de hectares. Para obter produtividade economicamente vi?vel da cultura, s?o utilizadas elevadas doses de fertilizantes nitrogenados. Tais fertilizantes possuem elevados custos economicos, podem contribuir para emiss?o de gases do efeito estufa e para polui??o de cursos de ?gua, al?m de infuenciarem de forma direta na decomposi??o da mat?ria org?nica do solo (MOS). Neste contexto, entender como ocorre a intera??o entre o nitrog?nio e a MOS no cultivo da cana ? importante tanto do vista economico quanto ambiental. Assim sendo o objetivo desse estudo foi avaliar a quantidade e qualidade do carbono do solo em fun??o de diferentes doses de nitrog?nio adicionado na forma de sulfato de am?nio no agroecossistema cana-de-a??car crua em Argissolo Amarelo de Tabuleiro Costeiro. O experimento foi instalado em canavial renovado em 2009, em ?rea cedida pela Usina LASA, no munic?pio de Linhares ? ES, em Argissolo Amarelo de textura arenosa/m?dia, no ambiente de Tabuleiros Costeiros. A variedade da cana-de-a??car (Saccharum spp.) utilizada foi a RB918639. Foram avaliados cinco tratamentos/doses de N-sulfato de am?nio quais sejam: 0 (testemunha), 80, 100, 120 e 160 kg ha-1 de N com quatro repeti??es, estabelecidos segundo delineamento experimental de blocos ao acaso. Cada unidade experimental (parcela) tinha 70 m? (5 linhas com 10 m, espa?adas 1,4 m). As amostras de planta e terra foram coletadas no m?s de setembro de 2014, correspondendo ? 4? soca. Os resultados indicaram que as doses de 100 e 120 kg, foram as mais eficientes para acumular o carbono nas fra??es h?micas, granulom?tricas, densim?tricas e nas fra??es do carbono oxid?vel. A dose de 160 kg foi a menos eficiente para acumular o carbono nas fra??es h?micas, granulom?tricas, densim?tricas e nas fra??es do carbono oxid?vel. O nitrog?nio total, a abund?ncia natural de 13C e 15N e a produtividade de colmo e palhada n?o apresentaram diferen?as significativas. Na composi??o elementar dos ?cidos h?micos (AH), as quantidades dos elementos qu?micos foram bem semelhantes entre as doses e coerentes com resultados na literatura para os AH. Para o coeficiente E4/E6 a dose de 160 kg de N foi a que apresentou o menor coeficiente E4/E6. Em rela??o ao infravermelho com transforma??o de Fourier verificou-se o predom?nio de grupamentos alif?ticos, e a analise de componentes principais possibilitou a separa??o clara do efeito das diferentes doses de N. No RMN C prevaleceram maiores quantidades de carbonos alif?ticos, isto foi confirmado com o ?ndice de alif?ticidade das amostras que foram superiores a 80 % para todas as amostras. Verificou-se tamb?m atrav?s do RMN 13C que a testemunha e a dose de 160 kg foram as que apresentaram menores ?ndices de aromaticidade. Portanto, conclui-se que os diferentes fracionamentos bem com as t?cnicas espectrosc?picas foram eficientes para avaliar a influencia das diferentes doses de N na decomposi??o da MOS.

Humic substances are macromolecules that naturally occur in all environments in which vegetation matter are present. In general, humic acid is part of humic substances which form the major fraction of the dissolved organic matters in surface water and represents 90% of dissolved organic carbon. Humic acid plays a fundamental role in many ecosystems since it interacts with toxic metal ions present in the system, resulting in a decrease in the bio-availability of such ions. Moreover, the availability of humic acid in water can react with other chemical compounds, such as chlorine to form trihalomethanes (including chloroform) and causes an increasing risk of cancer and may be linked to heart, lung, kidney, liver, and central nervous system damage. Therefore, humic acid removal in water treatment processes is very important in order to achieve the drinking water standards. Heavy metals are significant contaminants in aqueous system. All heavy metals can produce toxicity when ingested in sufficient quantities, but there are several important ones such as lead, mercury, copper, cadmium, arsenic, nickel and silver. These heavy metals are so pervasive and produce toxicity at low concentrations. Moreover, they may build up in biological systems and become a significant health hazard. / Adsorption is approved as an effective and simple method for water and wastewater treatment process. Many adsorbents then are developed for use in adsorption process such as montmorillonite, peat, activated carbon, etc. In this research, humic acid and heavy metals were mainly selected for adsorption study. In the sorption experiment, several adsorbents such as synthesised zeolite (SZ), natural zeolite (NZ), powdered activated carbon (PAC) and fly ash (FA), were selected to examine the application of HA and heavy metals both in individual and simultaneous adsorption, The characteristics and interactions of the adsorbents with HA and heavy metals were systematically studied by batch laboratory experiments. In the beginning, the adsorption of HA onto SZ, NZ, PAC and FA was investigated and their adsorption capacity was compared. The equilibrium adsorption of HA on SZ, NZ, PAC and FA was found to be 84.1, 67.8, 81.2 and 34.1 mg/g, respectively, at 30 oC and pH 5.0. Dynamic adsorption data show that these adsorbents could reach their adsorption equilibrium after 50 hours. From pH analysis, HA adsorption is favoured at low pH and an increase in pH will lead to the reduction of HA adsorption. SZ and NZ adsorption capacity were affected by the changing of solution temperature; however, in PAC and FA sorption study, there was no significant effect observed. Two heavy metal ions (Cu, Pb) removal by the adsorbents was then conducted. The results showed that the equilibrium sorption capacity of Cu and Pb ions on SZ, NZ, PAC and FA were 43.5, 24.2, 19.7, 28.6 and 190.7, 129.0, 76.8 mg/g, respectively at 30 oC and a pH value of 5. The appropriate pH for Cu and Pb removal was found to be 5 and 6. In most dynamic cases, these adsorbents needed at least 50 hours to reach the adsorption equilibrium. Only adsorption on FA required more than 150 hours to reach the equilibrium. / In simultaneous adsorption experiments, the influences of HA and heavy metal concentration (in the range of 10 to 50 mg/L for HA and 10 to 30 mg/l for heavy metals) on the HA-heavy metal complexation were investigated. The results demonstrated that increasing HA concentration mostly affected Cu adsorbed on SZ, FA and PAC and Pb adsorbed on SZ, NZ and PAC. For HA adsorption, the adsorption rate decreased rapidly with increased initial metal ion concentration. Moreover, the adsorption of heavy metals increased with increased heavy metals concentration in the presence of HA. In the presence of heavy metal ions, the order of HA adsorption followed PAC > FA > SZ > NZ. According to the results, the individual and simultaneous adsorption of HA and heavy metals on each adsorbent achieved a different trend. It mainly depended on the adsorption property of both adsorbates (HA and heavy metals) and adsorbents (SZ, NZ, PAC and FA) and also the operation factors such as pH, concentration, temperature and operation time. Even though this experiment could not obtain high adsorption performance, especially in coadsorption, as compared with other adsorbents, the adsorbents in this study represented a higher adsorption capacity and provide the potential for further development.

Immobilisierung bzw. Mobilisierung und Transport von Schadstoffen in der Umwelt, besonders in den Kompartimenten Boden und Wasser, sind von fundamentaler Bedeutung für unser (Über)Leben auf der Erde. Einer der Hauptreaktionspartner für organische und anorganische Schadstoffe (Xenobiotika) in der Umwelt sind Huminstoffe (HS). HS sind Abbauprodukte pflanzlichen und tierischen Gewebes, die durch eine Kombination von chemischen und biologischen Ab- und Umbauprozessen entstehen. Bedingt durch ihre Genese stellen HS außerordentlich heterogene Stoffsysteme dar, die eine Palette von verschiedenartigen Wechselwirkungen mit Schadstoffen zeigen. Die Untersuchung der fundamentalen Wechselwirkungsmechanismen stellt ebenso wie deren quantitative Beschreibung höchste Anforderungen an die Untersuchungsmethoden. Zur qualitativen und quantitativen Charakterisierung der Wechselwirkungen zwischen HS und Xenobiotika werden demnach analytische Methoden benötigt, die bei der Untersuchung von extrem heterogenen Systemen aussagekräftige Daten zu liefern vermögen. Besonders spektroskopische Verfahren, wie z.B. lumineszenz-basierte Verfahren, besitzen neben der hervorragenden Selektivität und Sensitivität, auch eine Multidimensionalität (bei der Lumineszenz sind es die Beobachtungsgrößen Intensität IF, Anregungswellenlänge lex, Emissionswellenlänge lem und Fluoreszenzabklingzeit tF), die es gestattet, auch heterogene Systeme wie HS direkt zu untersuchen. Zur Charakterisierung können sowohl die intrinsischen Fluoreszenzeigenschaften der HS als auch die von speziell eingeführten Lumineszenzsonden verwendet werden. In beiden Fällen werden die zu Grunde liegenden fundamentalen Konzepte der Wechselwirkungen von HS mit Xenobiotika untersucht und charakterisiert.<br> Für die intrinsische Fluoreszenz der HS konnte gezeigt werden, dass neben molekularen Strukturen besonders die Verknüpfung der Fluorophore im Gesamt-HS-Molekül von Bedeutung ist. Konformative Freiheit und die Nachbarschaft zu als Energieakzeptor fungierenden HS-eigenen Gruppen sind wichtige Komponenten für die Charakteristik der HS-Fluoreszenz. Die Löschung der intrinsischen Fluoreszenz durch Metallkomplexierung ist demnach auch das Resultat der veränderten konformativen Freiheit der HS durch die gebundenen Metallionen. Es zeigte sich, dass abhängig vom Metallion sowohl Löschung als auch Verstärkung der intrinsischen HS-Fluoreszenz beobachtet werden kann.<br> Als extrinsische Lumineszenzsonden mit wohl-charakterisierten photophysikalischen Eigenschaften wurden polyzyklische aromatische Kohlenwasserstoffe und Lanthanoid-Ionen eingesetzt. Durch Untersuchungen bei sehr niedrigen Temperaturen (10 K) konnte erstmals die Mikroumgebung von an HS gebundenen hydrophoben Xenobiotika untersucht werden. Im Vergleich mit Raumtemperaturexperimenten konnte gezeigt werden, dass hydrophobe Xenobiotika an HS-gebunden in einer Mikroumgebung, die in ihrer Polarität analog zu kurzkettigen Alkoholen ist, vorliegen. Für den Fall der Metallkomplexierung wurden Energietransferprozesse zwischen HS und Lanthanoidionen bzw. zwischen verschiedenen, gebundenen Lanthanoidionen untersucht. Basierend auf diesen Messungen können Aussagen über die beteiligten elektronischen Zustände der HS einerseits und Entfernungen von Metallbindungsstellen in HS selbst angeben werden. Es ist dabei zu beachten, dass die Experimente in Lösung bei realen Konzentrationen durchgeführt wurden. Aus Messung der Energietransferraten können direkte Aussagen über Konformationsänderungen bzw. Aggregationsprozesse von HS abgeleitet werden. / Transport and fate of xenobiotics in the environment, especially in water and soil, are of utmost importance for life on earth. A major reaction partner for xenobiotics in the environment are humic substances (HS). HS are degradation products of plant and animal tissue, which are formed in a combination of subsequent chemical and/or biochemical processes. Because of the complex history of their origin HS are extremely heterogeneous mixtures of different compounds. Consequently, they posses a great variety of interaction capabilities with various xenobiotics. The investigations of the fundamental interaction mechanisms between HS and xenobiotics make high demands on the analytical techniques used. Especially spectroscopic techniques are promising for the investigation of interaction mechanisms in complex systems. Luminescence spectroscopy has the great advantage of outstanding sensitivity and of multidimensionality, which in principle allows the investigation of HS under environmental relevant conditions. For the characterisation of interaction processes of HS with xenobiotics the intrinsic fluorescence of HS as well as the luminescence of extrinsic probes can be used.<br> The intrinsic HS fluorescence is determined by the molecular structure as well as the connection of the basic fluorophores. Conformational freedom as well as the presence of energy accepting groups in the neighbourhood of the fluorophores are highly important for the overall intrinsic HS fluorescence. The presence of metal ions can either quench or enhance the intrinsic HS fluorescence, which depends on the metal ion as well as on the origin of the HS investigated. While in most cases Al3+ ions enhance the intrinsic HS fluorescence, Ln3+ ions induce a fluorescence quenching.<br> Polycyclic aromatic hydrocarbons were used as extrinsic fluorescence probes in order to characterize the interaction of HS and hydrophobic organic xenobiotics. In investigations at ultra-low temperatures (10 K) it could be shown that pyrene is bound in a HS microenvironment with an polarity which resembles that of small alcohols (e.g., butanol).<br> In case of metal complexation, the lanthanide ions Eu3+ and Tb3+ were used as luminescence probes. Due to the outstanding luminescence properties of those ions, information about metal binding sites in HS were obtained. Based on the measurements of intramolecular and intermolecular energy transfer processes average distances of metal binding sites were deduced.

Many chemicals present in the aquatic environment can interfere with physiological functions in fish. Exposure to chemicals can be revealed by the use of biomarkers. Induction of 7-ethoxyresorufin O-deethylase (EROD) activity is a commonly used biomarker for exposure to CYP1A inducers such as dioxins and polyaromatic hyrdrocarbons. Vitellogenin is a frequently used biomarker for estrogenic compounds in various fish species whereas a biomarker for androgens, spiggin, is only found in sticklebacks. The main objectives of this thesis were to evaluate gill EROD activity as a biomarker and the three-spined stickleback as a model species in ecotoxicological studies. EROD activities were measured in gill, liver and kidney in rainbow trout (Oncorhynchus mykiss) caged in urban areas in Sweden. EROD induction was most pronounced in the gill. Also in fish caged at reference sites, with an expected low level of known CYP1A inducers, a marked gill EROD induction was found. One suggested inducer in rural waters is humic substances (HS). To evaluate the EROD-inducing capacity of HS, three-spined sticklebacks (Gasterosteus aculeatus) were exposed to HS of natural or synthetic origin. Both kinds of HS caused significant EROD induction. Gill EROD activities were also induced in sticklebacks exposed to ethynylestradiol (EE2) and β-naphthoflavone (βNF), alone and in combinations. Production of vitellogenin was induced in sticklebacks exposed to ≥50 ng EE2/l and a significant decrease in spiggin production was observed in individuals exposed to 170 ng EE2/l. Results from this thesis further strengthen the contention that gill EROD activity is a very sensitive biomarker for CYP1A inducers and that the stickleback is a suitable biomonitoring species, especially for exposure to CYP1A inducers. The finding that not only classical CYP1A inducers but also HS and high EE2 concentrations stimulate gill EROD activity is of significance for the interpretation of biomonitoring data.

Objective of this project was the study of interaction processes between humic substances, U(VI), Np(V) and kaolinite KGa-1b. It contributed to the attainment of a better process understanding, the improvement of the knowledge on the interaction of humic substances and metal ions and the enhancement of the thermodynamic database. With a synthetic humic acid (HA), N-containing functional groups of HA were characterized by 15N-NMR spectroscopy. Based on these results, model studies of the influence of amino groups on the complexation behavior of HA were performed. Spectroscopic studies with amino acids show that the amino group do not contribute to the U(VI) complexation at pH 4. The impact of kaolinite on the formation of HA and humic substance-kaolinite-sorbates was studied in model syntheses. The results exhibit that the presence of kaolinite during the syntheses mainly influences the yields on HA and their elemental compositions. Synthetic humic substance-kaolinite-sorbates were isolated. Under exclusion of CO2, the U(VI) complexation by HA was investigated at pH 7 by means of the conventional time-resolved laser-induced fluorescence spectroscopy (TRLFS) and TRLFS with ultrafast pulses. Complexation parameters for the ternary complex UO2(OH)HA(I) were determined. Studies of the Np(V) reduction in presence of HA with different functionalities under anaerobic conditions have shown that Np(V) is reduced to Np(IV) by HA. The redox capacity depends on the HA functionality. Applying a modified HA it was verified that phenolic/acidic OH groups play a dominating role in the Np(V) reduction. The influence of HA on the U(VI) and Np(V) sorption onto kaolinite was investigated in batch experiments. In dependence on the experimental conditions, HA effects the sorption and consequently the mobility of U(VI) and Np(V). From studies of the U(VI) sorption onto synthetic humic substance-kaolinite-sorbates it was concluded that the structure and functionality of sorbed/associated humic substances considerably influence the sorption behavior of U(VI). The structure of U(VI)-kaolinite-surface complexes in presence of HA was studied by means of X-ray absorption spectroscopy and TRLFS and compared to those of U(VI)-kaolinite-complexes. Investigations of the migration of HA and U(VI) in the laboratory system kaolinite-water were carried out in diffusion experiments. The migration of HA in compacted clay is governed by diffusion and influenced by its colloidal properties. Humic substances exert an immobilizing effect on the U(VI) transport in compacted kaolinite.