Os Vertissolos apresentam alto potencial para a produção agrícola e para estocar carbono. No entanto, diversos aspectos sobre sua gênese, fundamentais para qualidade e sustentabilidade do solo, permanecem incompreendidos. As várias lacunas sobre suas características particulares estão relacionadas ao incomum teor de alumínio trocável; a manifestação de feições morfológicas e vérticas em uma matriz inorgânica dominada por fases cauliníticas; e a preservação e estoque de carbono em condições climáticas de semiárido e temperado. Dessa forma, os objetivos deste estudo foram (i) investigar a gênese de um Vertissolo ácido, bem como os fatores e mecanismos da geração dessa acidez, (ii) compreender o papel dos interestratificados no desenvolvimento das feições vérticas em Vertissolo com predomínio de caulinita na fração argila, e (iii) investigar os fatores e mecanismos que promovem a gênese de Vertissolos Ebânicos sob diferentes condições climáticas no Brasil. Amostras de seis perfis de Vertissolos foram utilizadas, sendo quatro Ebânicos e dois Háplicos, ambos localizados entre as regiões nordeste, sudeste e sul do Brasil. Análises morfológica, físicas, químicas, mineralógicas e isotópicas foram realizadas. Na modelagem dos difratogramas foi utilizado o programa Newmod. Para identificação dos grupos funcionais orgânicos do solo realizou-se a ressonância magnética nuclear da fração ácido húmico, e a subtração espectral. Todos os Vertissolos apresentaram textura de argilosa a muito argilosa, consistência seca variando de dura a extremante dura e consistência molhada entre muito plástica e muito pegajosa. Os valores de pH variaram entre ácido e alcalino. Foram eutróficos, com predomínio de cálcio no complexo de troca na maioria dos perfis. O teor de carbono reduziu em profundidade, não mascarou o potencial de contração e expansão, e promoveu melhorias na agregação, principalmente nos horizontes superficiais. Houve autigênese de minerais, os minerais primários predominaram nas frações areia e silte, e na fração argila espécies de esmectitas dioctaedrais. Independente da espécie esmectítica e do tipo de vegetação (plantas C3 e/ou C4) houve maior diversidade de grupos funcionais nos horizontes superficiais. O mecanismo de estabilização do carbono nos Vertissolos Ebânicos ocorreu por meio da interação entre as fases inorgânicas e orgânicas, mediada por pontes de cátions polivalentes não metálicos e metálicos, e também por interação eletrostática entre os constituintes inorgânicos e orgânicos. A manifestação das feições morfológicas e vérticas no Vertissolo com predomínio de caulinita na fração argila foi gerada pelos interestratificados caulinita-montmorilonita resultantes da perda da lâmina tetraedral das esmectitas via transformações no estado sólido. A acidez no Vertissolo ácido foi gerada pela hidrólise e dissolução das fases minerais mediados por um clima passado mais úmido e continuado pelo clima atual úmido, sendo os teores de alumínio trocável naturais. Nesse contexto, esse estudo contribui com avanços na gênese, mineralogia e mecanismos de estabilização do carbono no solo, os quais são temáticas relevantes desse milênio e contribui a outras áreas cientificas. / Vertisols have high potential for agricultural production and for carbon stocking. However, several aspects about its genesis, fundamental to soil quality and sustainability, remain misunderstood. The various gaps on its particular characteristics are related to the unusual exchangeable aluminum content; the manifestation of morphological and vertic features in an inorganic matrix dominated by kaolinitic phases; and the preservation and stocking of carbon in semi-arid and temperate climatic conditions. Thus, the aims in this study were to (i) investigate the genesis of an acidic Vertisol, as well as the factors and mechanisms of the acidity generation, (ii) understand the role of the interstratified clay minerals in the development of vertic features in a kaolinitic Vertisol, and iii) investigate the factors and mechanisms that promote the genesis of Pellic Vertisols under different climatic conditions in Brazil. Samples of six profiles of Vertisols were used, being four Pellic and two Haplic, both located between the northeast and southern regions of Brazil. Morphological, physical, chemical, mineralogical and isotopic analyzes were performed. In the modeling of the diffractograms, the Newmod program was used. For the identification of the organic functional groups of the soil, the nuclear magnetic resonance of the humic acid fraction and the spectral subtraction were performed. All the Vertisols presented a texture of clayey to very clayey, dry consistency ranging from hard to extremely hard and wet consistency between very plastic and very sticky. The pH values varied between acid and alkaline. They exhibit high base saturation, with the predominance of calcium in the exchangeable complex in most of the profiles. The carbon content reduced in depth; did not overlap the shrinking-swelling potential; and promoted improvements in aggregation, especially in the upper horizons. There was autigenesis of minerals, primary minerals predominated in the sand and silt fractions, and in the clay fraction species of dioctahedral smectites. Regardless of the smectic species and the type of vegetation (C3 and/or C4 plants), there was a greater diversity of functional groups in the superficial horizons. The mechanism of carbon stabilization in the Pellic Vertisols occurred through the interaction between inorganic and organic phases, mediated by bridges of non-metallic and metallic polyvalent cations, and by electrostatic interaction between inorganic and organic constituents. The manifestation of the morphological and vertic features in the kaolinitic Vertisol was generated by the interstratified kaolinite-montmorillonite resulting from the loss of the tetrahedral sheet of smectites by solid-state transformations. The acidity in the acid Vertisols was generated by the hydrolysis and dissolution of the mineral phases mediated by a humid past climate and continued by the current humid climate, being the exchangeable aluminum contents natural. In this context, this study contributes to advances in the genesis, mineralogy, and mechanisms of soil carbon stabilization, which are relevant themes of this millennium and contribute to other scientific areas.

Em regiões agrícolas próximas dos grandes centros urbanos e onde há o uso intensivo de recursos naturais, em especial do solo, a reciclagem para fins agrícolas de lodos de esgotos aparece como alternativa promissora. Contudo, a sustentabilidade dessa prática deve ser avaliada, ainda mais se considerado a escassez de informações sobre possíveis impactos ambientais em áreas tropicais. Com esse objetivo esse trabalho avaliou os efeitos da adição de lodo de esgoto em dois solos, Latossolo Vermelho eutroférrico e Latossolo Vermelho distrófico, coletados no 7º ano de um experimento em campo, instalado em 1997 na Faculdade de Ciências Agrárias e Veterinárias da Unesp, em Jaboticabal-SP. O lodo de esgoto foi proveniente da Estação de Tratamento de Esgoto da Companhia de Saneamento Básico do Estado de São Paulo, em Barueri-SP. Para observar os efeitos da adição do lodo de esgoto foram analisados os ácidos húmicos extraídos dos solos utilizando absorção de radiação no UV-Visível, infravermelho com transformada de Fourier, ressonância magnética nuclear, ressonância paramagnética eletrônica, fluorescência e análise elementar. Para a análise do solo intacto utilizou-se a fluorescência induzida por laser, e para as frações físicas e químicas a emissão atômica com plasma indutivamente acoplado. Experimentos de infravermelho com transformada de Fourier e ressonância magnética nuclear forneceram espectros com bandas características de grupos alifáticos para o ácido húmico extraído do lodo, comprovando seu alto grau de alifaticidade. O nível de radicais livres do tipo semiquinona determinado por ressonância paramagnética eletrônica diminuiu significativamente para os solos submetidos à adição de lodo. Dados de fluorescência utilizando diferentes metodologias (Zolnay et al., 1999; Milori et al., 2002; Kalbitz et al., 1999) e fluorescência induzida por laser, de amostras de solo intacto, apresentaram comportamento similar. De forma geral, os resultados obtidos por análises espectroscópicas mostraram à incorporação de compostos menos humificados, com um alto grau de alifaticidade e baixo grau de aromaticidade. A análise de metais em solos tratados com lodo de esgoto em algumas situações não tem evidenciado o aumento destes elementos, mesmo quando o lodo apresenta níveis superiores aos valores encontrados no solo. Assim fica a pergunta, onde e como estão os metais pesados oriundos do lodo e que deveriam ser detectados em níveis maiores nos solos tratados. Neste trabalho procuramos ampliar as avaliações para além dos procedimentos convencionais com análises das frações físicas e químicas. Os metais pesados estudados foram: Cd, Cr, Cu, Fe, Co, Mn, Mo, V e Zn. Os resultados obtidos mostraram maior afinidade dos metais pelas frações físicas de menor tamanho (argila e silte fino). Contudo, maiores teores de metais foram observados nas frações químicas do solo, sugerindo maior poder de complexação das substâncias húmicas do solo. A concentração de Zn observada na água de lavagem da humina foi superior a encontrada na fração humina, mostrando maior afinidade desse metal pela matéria orgânica dissolvida. Esse resultado é importante, pois evidencia a perda desse metal durante o processo de fracionamento químico, visto que essa água é descartada. As frações de ácido fúlvico 1 e 2 apresentaram concentrações significativas de metais, principalmente Cd, Cu, Mn e Zn, sendo as maiores encontradas para o ácido fúlvico 1. O ácido húmico, devido a grande quantidade de grupos reativos (carboxílicos e fenólicos), mostrou ser um forte agente complexante de metais. Esses resultados indicam diferente afinidade dos metais pelas frações físicas e químicas do solo, ressaltando a importância do estudo do destino dos metais nas diferentes frações do solo. / In agricultural regions near big urban areas and where the intensive use of natural resources exists, in particular of the soil, recycling sewage sludge with agricultural finality appears as a promising alternative. However, the sustainability of this practice needs to be further assessed, even more so when considering there is lack of information on environmental impacts in tropical areas. The present work evaluated the effects of sewage sludge addition to two soils, Rhodic Eutrodox and Rhodic Hapludox by FAO Taxonomy) colleted from a field experiment, installed in 1997 in the city of Jaboticabal, São Paulo State. Sewage sludge was obtained from the Barueri sewage sludge treatment plant, located in the metropolitan region of São Paulo State, Brazil, operated by the Basic Sanitation Company of the State of São Paulo. In order to observe the effects of the sewage sludge addition, the humic acids extracted from soils were analyzed by absorption of ultraviolet and visible radiation, Fourier transform infrared, nuclear magnetic resonance, eletronic paramagnetic resonance, fluorescence and elementar analyses. To analyse the intact soil laser induced fluorescence was used, and for physics and chemical inductively coupled plasma atomic emission was used. The results obtained by Fourier transformed infrared and nuclear magnetic resonance showed spectra with characteristic bands from aliphaticity groups for humic acid from sewage sludge, confirming their high aliphacitity degree. The level of the semiquinona free radicals determined by electronic paramagnetic resonance decreased for soils under sewage sludge application. Data from fluorescence utilizing different methodologies (Zolnay et al., 1999; Milori et al., 2002; Kalbitz et al., 1999) and laser induced fluorescence, from intact soil, showed similar results. In a general manner, the results obtained for spectroscopy analyses showed incorporation of less humified compounds, with high aliphaticity degree and lower aromaticity degree. Analyses of the metals in soils under sewage sludge application in some cases have not evidenced the increase of these elements, even when the sewage show higher levels to those found in the soils. Thus, the question remains, where and how are the heavy metals from sewage sludge? Which, should have been detected in higher levels in soils under sewage sludge application? The objective of this work was to amplify the valuations beyond the conventional proceedings with analyses of physics and chemical fractions. The heavy metals studied were: Cd, Cr, Cu, Fe, Co, Mn, Mo, V and Zn. The results obtained showed higher affinity of metals for physical fractions that have smaller size (clay and fine silt). However, higher heavy metals concentrations were observed in the chemical fractions of the soils, due to higher complexity power of the humic substances of soils. The Zn concentration observed in the water of the humin wash was higher than what was observed in the humina fraction, showing higher affinity of this metal for dissolved organic matter. This result is important, because it evidences the loss of this metal during the extraction process of the humic substances, since this water is discarded. The fractions of fulvic acids 1 and 2 showed significative concentrations of the metals, mainly Cd, Cu, Mn and Zn, being that the biggest were for humic acids, because the most quantity of the reactive groups (charboxilics and phenolics), showed to be a strong complex agent of the metals. Such results indicate different affinity of metals for physics and chemical fractions from soils, emphasizing the importance of the study of the course of heavy metals in the different fractions of the soil.

A Bacia hidrográfica do Rio Sorocá-Mirim encontra-se no Planalto de Ibiúna, que faz parte de um conjunto de blocos falhados formando grábens e meio grábens, que compõem um sistema de bloqueio estrutural onde a água é aprisionada em sub superfície criando as condições ideais para a formação de turfeiras. Características como a geometria dos interflúvios, a assimetria das vertentes e das planícies de inundação e também a disposição da rede de drenagem, denotam a grande influência das estruturas geológicas nesta bacia hidrográfica. As zonas de acumulação de matéria orgânica encontradas na Bacia do Sorocá-Mirim estão vinculadas à ambientes fluviais particulares, relacionados ao controle estrutural, que é característica marcante da área. O presente trabalho teve como objetivo estudar turfeiras, em dois ambientes fluviais diferentes (terraço e anfiteatro) em relação às suas características físicas, químicas, orgânicas e sua distribuição areolar para entender como a formação destas turfeiras foi influenciada por esses ambientes. O levantamento topográfico das duas áreas, assim como uma série de ensaios e análises laboratoriais demonstraram que as turfeiras dos dois ambientes apresentam idades diferentes em aproximadamente 1000 anos (turfeira da área 2, terraço, mais antiga do que a turfeira da área 1, anfiteatro), mesmo tipo de plantas acumuladas ao longo destes anos e diferenças principalmente no que se refere à posição preferencial ao acúmulo da matéria orgânica e à variações, no sentido das maiores profundidades, de diversos parâmetros observados. Verificou-se que a área 1 sofreu maiores alterações do modelado, e consequentemente nas suas condições hidrológicas ao longo dos tempos, passando a ser um ambiente mais drenado, mais oxigenado, com uma turfeira que apresentou resultados laboratoriais mais heterogêneos, com concentrações de matéria orgânica e dos elementos vinculados a ela, variando bastante ao longo da feição. A área 2 não sofreu grandes alterações no modelado, mantendo-se mais úmida ao longo do tempo o que acarretou em uma turfeira mais homogênea com valores mais constantes de matéria orgânica e dos elementos vinculados a ela, ao longo da feição. Essas diferenças são reflexo da influência do modelado nos processos de acumulação da matéria orgânica, onde em cada feição (terraço, ou anfiteatro) a matéria orgânica é acumulada em posições específicas, sofrendo maior ou menor interferência de materiais minerais adjacentes; e principalmente o modelado controla as condições hidrológicas, diferentes, em cada uma das feições, fazendo com o que o ambiente seja mais ou menos úmido e desta forma sendo o elemento principal de controle dos processos de evolução da matéria orgânica. / The Sorocá-Mirim River basin is located on the Ibiúna Plateau, wich is part of a set of failed blocks forming grabens and half grabens, which makes up a structural block system where water is trapped in sub-surface creating the ideal conditions for the formation of peatlands. Characteristics such as the geometry of interfluves, the asymmetry of slopes and flood plains and also the layout of the drainage network, denote the great influence of the geological structures in this basin. The areas of accumulation of organic matter found in the Sorocá-Mirim Basin are linked to particular fluvial environments, related to structural control, which is a characteristic feature of the area. The present study aimed to study peatlands in two different fluvial environments (terrace and amphitheater) in relation to their physical, chemical, and organic characteristics and their areolar distribution to understand how the formation of these peatlands was influenced by these environments. The topographic survey of the two areas, as well as a series of laboratory tests and analyzes showed that the peatlands of the two environments present different ages in approximately 1000 years (peatland of area 2 older than the peatland of area 1), same type of plants, accumulated along these years and differences mainly with respect to the preferential position to the accumulation of the organic matter and the variations, in the direction of the greater depths, of several observed parameters. It was verified that area 1 underwent major alterations in the landform, and consequently in its hydrological conditions over time, becoming a more drained, more oxygenated environment, with a peatland that presented more heterogenous laboratory results, with concentrations of organic matter and the elements attached to it, varying greatly throughout the feature. Area 2 did not undergo major alterations in the landform, remaining wetter over time which resulted in a more homogeneous peat with more constant values of organic matter and the elements bound to it, along the feature. These differences reflect the influence of landform on the processes of organic matter accumulation, where in each feature (terrace or amphitheater) the organic matter is accumulated in specific positions, suffering more or less interference of adjacent mineral materials; and mainly the landform controls the different hydrological conditions in each of the features, making the environment more or less moist and thus being the main element of control of the evolution processes of organic matter. The work showed that landform is the main conditioning element of the humidity of the environments and consequently of the processes of evolution and the characteristics of the peatlands.

Humic substances (HS), the complex mixture of organic molecules produced by microbial and abiotic degradation of plant and animals residues, are the major components of organic matter in soil and natural waters. As such, they are vital to the integrity of soil, play important roles in nutrient biogeochemical cycling and determine the mobility and fate of both nutrients and contaminants. How HS enact their varied roles, however, is largely unknown due to the lack of comprehension of their molecular make-up. What is known is that they contain aromatic (e.g. phenols, condensed aromatics) and aliphatic (e.g. carbohydrates, lipids) molecules with prevailing carboxyl and hydroxyl functionalities. As for other complex chromatographically inseparable mixtures, high-resolution analytical techniques such as Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) as well as Nuclear Magnetic Resonance (NMR) spectroscopy have been applied to study HS composition at the molecular level. While FT-ICR MS can provide molecular formulae, it is only NMR that can unveil structures. Until now, however, very few unambiguous structures of individual molecules have emerged from standard NMR experiments. This is because purposely designed multidimensional NMR experiments are required to achieve ‘spectroscopic separation’ where chromatography fails. In this work, ‘spectroscopic separation’ was accomplished with the aid of chemical modification in the form of 13C methylation of COOH and OH groups. 13C containing tags allow the observation of signals only from molecules carrying these tags. In combination with purposelydesigned isotope-filtered NMR experiments, these tags act as spies reporting on their surrounding structure. This is achieved by utilising scalar and dipolar couplings to transfer the polarisation between protons and carbons of the 13CH3O groups and nuclei of the parent molecules. The necessary spectral resolution is attained using 3D/4D NMR experiments. This approach provides access to an array of correlated chemical shifts of HS molecules and represents a paradigm shift in the use of tags in investigations of complex mixtures: instead of focusing only on the tags, they are used to obtain structural information from the molecules they are attached to. The compounds at the centre of this investigation are the phenols of HS. These molecules are thought to be important in many of the key processes in organic matter rich soils, particularly peat. For example, their accumulation is thought to impair the activity of extracellular enzymes essential for the degradation of peat HS. Understanding the nature and source of phenols would provide a more fundamental framework for rationalising their role in peat, as well as other carbon rich soils. The developed methodology was initially tested on model mixtures containing 3 or 9 phenolic compounds before applying it to a operational fraction of HS, fulvic acid, extracted from a Scottish raised peat bog. For this fulvic acid, over 30 major phenolic molecules/moieties were identified, many of which can be directly traced to the flora prevalent in the vicinity of the sampling site. For the first time in 150 years of HS research, a novel analytical methodology has yielded unambiguous structural information, providing the first steps towards understanding the various roles of HS in natural systems.

Os hidrocarbonetos policíclicos aromáticos (HPA) são poluentes formados por dois ou mais anéis aromáticos que podem causar efeitos mutagênicos, carcinogênicos e teratogênicos aos seres humanos. Os HPA não são suscetíveis à degradação pela maioria dos micro-organismos devido a sua baixa solubilidade em água e a sorção destes poluentes na parte mineral e orgânica do solo. Uma forma de tratamento é o uso de processos oxidativos que podem degradar inúmeros contaminantes orgânicos e minerizá-los a gás carbônico e água. Neste trabalho foi avaliada a eficiência da degradação do isômeros fenantreno e antraceno, dois tipos de HPA, em areia padrão, utilizando-se como oxidantes o permanganato, peróxido de hidrogênio e persulfato ativado. De acordo com a matriz e o contaminante, após 24 horas de tratamento, verificou-se a degradação de 95 a 98% utilizando-se como oxidantes permanganato e de 34 a 62% utilizando-se a reação de Fenton. Foi identificada a antraquinona como produto do antraceno, independentemente do oxidante utilizado. Dentre os oxidantes, avaliou-se o persulfato ativado com ferro para a aplicação em solos arenosos contaminados com HPA. Quando se utilizou persulfato ativado com ferro em areia padrão houve a decomposição, após 24 horas de tratamento, de 60 e 95%, de fenantreno e antraceno, respectivamente. Em solos arenosos utilizando-se o persulfato, a degradação dos contaminantes foi predominantemente inferior devido ao possível efeito de matriz. Em contrapartida praticamente não houve a decomposição das substâncias húmicas. Esta é característica favorável, pois não houve a competição da matéria orgânica com o contaminante pelo persulfato, além de não promover alterações no teor de carbono presente no solo / Polycyclic aromatic hydrocarbons (PAH) are pollutants formed by two or more aromatic rings that can be mutagenic, carcinogenic and teratogenic to humans. PAH do not undergo degradation by most microorganisms due to this low water solubility and adsorption in the mineral and organic soil phase. One form of treatment is the use of oxidative processes that can degrade numerous organic contaminants and mineralize them to carbon dioxide and water. In this study, it was evaluated the efficiency of phenanthrene and anthracene degradation, in standard sand soil using permanganate, hydrogen peroxide and activated persulfate as oxidants. Depending on the contaminant and the matrix, over 24h of treatment, it was found the degradation 95 to 98% using permanganate and 34 to 62% using reaction Fenton. Anthraquinone was identified as product of anthracene, independent of the oxidant used. Among the oxidants, persulfate activated with iron was evaluated in the degradation of PAH in sandy soils. In standard sand, this process promoted,over 24 hours of treatment, a degradation level up to 60 % phenanthrene and 95% for anthracene. In sand soils, the degradation of the contaminants was lower due to possible matrix effect. In constrast there was no decomposition of humic substances, indicating no competition between the organic matter and the PAH by persulfate, and no change in the soil carbon content

Les BioRéacteurs à Membranes (BàM) sont une technologie adaptée à l’un des challenges du 21ème siècle : la réutilisation des eaux usées.En combinant un traitement biologique et une filtration membranaire, ce procédé permet d’atteindre une qualité d’eau adaptée à la réutilisation en permettant une désinfection physique totale. Néanmoins, son essor économique est fortement limité par le colmatage membranaire qui, quand le système est optimisé, est dû principalement à la Matière Organique Dissoute (DOM). Afin de comprendre et de maitriser ce colmatage, des outils ont été développés pour identifier les composés de la DOM responsables du colmatage. Ainsi, au cours de cette thèse, la DOM de deux BàM, alimentés par des effluents réels, a été étudiée ; un BàM traitant des eaux usées urbaines(station d’épuration de La Grande Motte) et un BàM échelle pilote traitant des urines réelles. La matière organique dissoute issue du premier BàMa ainsi été fractionnée par taille et par hydrophobicité pour identifier les mécanismes de colmatage associés à chaque fraction.Des tests de filtration, réalisés sur les différentes fractions, ont permis d’identifier les colloïdes (protéines) comme responsables majeurs du colmatage externe (gâteau) et les substances humiques comme responsables du colmatage interne. En combinant ces tests de filtration avec des mesures de fluorescence3D (3DEEM), étant une méthode rapide dont le signal facilement exploitable, il a été possible de définir des indicateurs qualitatifs pour ces deux familles de colmatants. Par la suite, en combinant la 3DEEM avec une méthode de séparation et quantification par taille (LC-OCD), le signal de 3DEEM qualitatif a été calibré pour donner une information quantitative et de taille au travers d'une analyse rapide.Ces nouveaux indicateurs ont ensuite été mesurés sur site et ont permis d’établir des liens entre les paramètres opératoires ou la qualité de l’intrant pour le suivi global de la DOM et son impact sur le colmatage. Ces outils soulignent toute la potentialité de la fluorescence 3D comme indicateur en temps réel du suivi, du contrôle et de l’optimisation de l‘étape de séparation membranaire. / Membrane BioReactors (MBR) are suitable technology to face one of the major 21th century challenges : wastewater reuse.Combining biological treatment with membrane separation step, MBR produce reusable water through total physical disinfection. Nevertheless, it democratization is limited by membrane fouling that is mainly caused by Dissolved Organic Matter (DOM) compounds when the system is optimized.In order to understand and control membrane fouling, tools were developed to identify DOM compounds responsible for this phenomenon.Thus, this PhD work, focused on studying the DOM taken from two MBR fed with real wastewater: a full-scale MBR treating urban wastewater (La Grande-Motte wastewaster treatment plant) and a lab-scale MBR treating urine from source-separated toilets.Dissolved organic matter collected in the first MBR was fractionated by size and hydrophobicity to identify fractions’ fouling mechanisms. Then, filtration tests performed on the different fractions highlighted the role of colloids (proteins) in external fouling (cake) and humic substances in internal fouling. Filtration tests were combined with fluorescence3D (3DEEM) measurements, which is a quick identification method with an easy extracted signal, allowing to define qualitative indicators for both foulants classes.After, coupling 3DEEM with a size separation and quantification method (LC-OCD), qualitative signals from foulants indicators were calibrated. Thus, using 3DEEM it was possible to obtain a quantitative and size information about DOM foulants. These new indicators were used on-site and allowed establishing links between DOM and operating parameters or influent quality, which is necessary for DOM global control and its impact on membrane fouling. These tools highlight the potentiality for 3DEEM on-line application for separation step monitoring, control and optimization.

A Bacia do Araripe, conforme Brito Neves et al. (2000), está inserida na unidade geotectônica da Província Borborema, abrangendo os estados do Ceará, Pernambuco e Piauí. Este trabalho buscou identificar possíveis intervalos potencialmente geradores da Formação Santana (Aptiano-Albiano) na Bacia do Araripe, a partir de técnicas de geoquímica e petrografia orgânica para caracterizar dez amostras de campo, referentes a folhelhos orgânicos provenientes deste intervalo estratigráfico. Os valores de COT indicam que todas as amostras possuem mais que o mínimo de carbono orgânico necessário para geração de hidrocarbonetos, a partir de 1 % em massa. Foram encontrados valores no pico S2 que variam de 7,44 a 13,56 mg HC/g de rocha para os Membros Crato e Romualdo (base e topo da Formação estudada), conferindo-lhes um potencial petrolífero bom e muito bom, respectivamente. No Membro intermediário, Ipubi, há um acréscimo na produção de hidrocarbonetos rumo ao seu topo estratigráfico, mas ocorre também a amostra com mais pobre potencial petrolífero, a amostra 9, com valor de S2 de 0,05 mg HC/g de rocha. O tipo de querogênio é classificado como tipo II para os Membros Crato e Romualdo, e tipos I, II e III para o Membro Ipubi. Os valores de ICE variam entre 3.0 a 4.0 (Robertson Research Limited), e de Tmax (361 a 433 ºC), permitindo classificar as amostras como imaturas a marginalmente maturas, conforme classificação de Peters & Cassa (1994) Foram encontradas vitrinitas apenas no Membro Ipubi, indicando material imaturo com 0,29 – 0,48% Rrandom, e baixo grau de maturação 0,60% Rrandom na amostra 2. A petrografia sob luz refletida mostra que as amostras 2, 3 e 9 estão contaminadas por betumen, interferindo nos valores de índice de produção, além de reflectância da vitrinita para a amostra 9. Análises de DRX mostram que o quartzo é o mineral mais abundante nas amostras, seguido pela esmectita e calcita, por vezes gipso, pirita e ilita e raramente caolinita. A petrografia sob luz transmitida, indica a matéria orgânica amorfa, como sendo o principal componente do querogênio estudado, seguido por fitoclastos e palinomorfos. A Análise elementar das razões atômicas de N, C, H e S, apontam os maiores valores nas amostras 5 a 8 (Membro Ipubi), podendo relacioná-las também aos maiores valores de COT e pertencentes a querogênio do tipo I, o menor valor dos parâmetros supracitados ocorre na amostra 9, a única que possui querogênio do tipo III. Os valores intermediários encontrados nas amostras 1 a 4 e 10, coincidem com amostras referentes a querogênio do tipo II. O intervalo em que se observa maior predominância destas condições está localizado no topo do Membro Ipubi, englobando as amostras 5 a 8. Foi determinado, a partir das análises realizadas, que este grande intervalo é caracterizado como o maior potencial gerador de petróleo identificado neste trabalho, apesar das amostras analisadas estarem imaturas. / The Araripe Basin, according to Brito Neves et al. (2000), is inserted in the geotectonic unit of the Borborema Province, covering the states of Ceará, Pernambuco and Piauí. This study aimed to identify possible potentially generating intervals of the Santana Formation (Aptian-Albian) in the Araripe Basin, from geochemical techniques and organic petrography to characterize ten samples field, referring to organic shales from this stratigraphic interval. The COT values indicate that all samples have more than the minimum of organic carbon required for generation of hydrocarbons, from 1% by mass. The S2 values ranging from 7.44 to 13.56 mg HC / g of rock for the Crato and Romualdo Members (base and top of the study Formation), giving them a good petroleum potential and very good, respectively. In the intermediate member, Ipubi, there is an increase in production of hydrocarbons toward its top stratigraphic, but also occurs the sample with poorer oil potential, the sample 9, with a value of S2 0.05 mg HC / g rock. The type of kerogen is classified as type II for Members Crato and Romualdo, and types I, II and III to the Member Ipubi. SCI values range from 3.0 to 4.0 (Robertson Research Limited), and Tmax (361-433 °C), allowing classifying the samples as immature to marginally mature, as Peters & Cassa classification (1994). Vitrinitas were found only in the Member Ipubi indicating immature material with from 0.29 to 0.48% Rrandom and low degree maturity 0.60% Rrandom the sample 2 The petrographic under reflected light shows that samples 2, 3 and 9 are contaminated with bitumen, interfering with the production index values, and the vitrinite reflectance for sample 9. XRD analysis shows that quartz is the most abundant mineral in the samples, followed by the smectite and calcite sometimes gypsum, pyrite and illite and kaolinite rarely.The petrographic under transmitted light, indicates the amorphous organic material as the main component of kerogen studied, followed by phytoclasts and palinomorphs. The Analysis of the atomic ratios of N, C, H and S, indicate the highest values in samples 5-8 (Member Ipubi), associated also to higher TOC values and belonging to Type I kerogen, the lowest value the above parameters occurs in the sample 9, the one that has the type III kerogen. Intermediate values found in samples 1 to 4 and 10 matching samples related to type II kerogen. The interval in which there is a predominance of these conditions is located at the top of the Member Ipubi, encompassing the samples 5 to 8. It was determined from the analyzes carried out, this long interval is characterized as the greatest potential for generating oil identified in this work although of the samples are immature.

Resumo: O objetivo deste trabalho foi analisar a composição química do solo (M.O, CTC e H+Al), em cinco camadas (0-20, 20-40, 40-60, 60-80 e 80-100 cm), com 18 cultivares da cana-de-açúcar. O experimento foi realizado na Fazenda de Ensino e Pesquisa da FCAV/UNESP, localizada no Município de Jaboticabal, Estado de São Paulo. O experimento foi instalado em um Latossolo-Vermelho Escuro, eutrófico, A moderado, textura muito argilosa - EUTRUSTOX. Nas camadas (0-20, 20-40, 40-60, 60-80 e 80-100 cm) foram coletadas 03 subamostras dos solos que, depois foram submetidas à análise química para fins de fertilidade, as quais foram realizadas pelo Laboratório de Análise de Solo do Departamento de Solos e Adubos da FCAV. Foram realizados três experimento com delineamento experimental em blocos casualizados com 6 cultivares e 3 epocas, em esquema fatorial 6x3, com 3 repetições para cada cultivar. Os tratamentos principais foram composto por 6 cultivares precoces, 6 cultivares médias e 6 cultivares tardias e o secundário as 3 épocas analisadas (12, 15 e 17 meses). Nas cultivares precoces os valores de CTC no solo acompanharam todos os resultados da matéria orgânica, apresentando redução dos valores ao longo das épocas analisadas. Relação inversa foi obtida pela acidez potencial. Nas cultivares médios, o solo com a cultivar IACSP94-4004 se destacou, apresentando os maiores teores de matéria orgânica e menor teor de acidez potencial, além de obter elevados valores de CTC na camada superficial do solo. Enquanto que para as cultivares tardias os valores de CTC no solo acompanharam todos os resultados da matéria orgânica, apresentando redução dos valores ao longo das épocas analisadas. A acidez potencial aos 17 meses apresentou maiores valores em toda camadas analisadas / Abstract: The aim of this study was to analyze the chemical composition of soil (organic matter, CEC and H + Al) in five layers (0-20, 20-40, 40-60, 60-80 and 80-100 cm) with 18 cultivars of cane sugar. The experiment was conducted at the Teaching and Research Farm, FCAV / UNESP, located in Jaboticabal, São Paulo. The experiment was installed in a dystrophic, dark red, well-nourished, moderate, clayey - EUTRUSTOX. Layers (0-20, 20-40, 40-60, 60-80 and 80-100 cm) were collected 03 subsamples of the soils that were later subjected to chemical analysis for fertility, which were performed by the Laboratory of Soil Analysis, Department of Soils and Fertilizers of FCAV. We conducted three experiments with randomized complete block design with six cultivars and three epochs in 6x3 factorial design with three replications for each cultivar. The main treatments consisted of 6 early cultivars, six medium and six cultivars late cultivars and the three secondary sampling seasons (12, 15 and 17 months). In the early cultivars in the soil CEC values followed all the results of organic matter, a reduction of the values along the studied periods. Inverse relationship was obtained by the potential acidity. Cultivars, the average soil with cv IACSP94-4004 stood out, with higher organic matter content and lower acidity potential, and achieve high CEC values in the topsoil. While for the late cultivars in the soil CEC values followed all the results of organic matter, a reduction of the values along the studied periods. The potential acidity at 17 months was highest in all layers analyzed / Orientador: Marcos Omir Marques / Coorientador: Luis Carlos Tasso Júnior / Banca: Wilson José Oliveira de Souza / Banca: Fábio Olivieri de Nobile / Banca: José Marques Junior / Banca: Rouverson Pereira da Silva / Doutor

<p>Cover crop use, especially in no-till systems, is an evolving practice to maintain or improve soil health. There are many possible indicators of soil health, but this study focuses on the analysis of soil aggregate stability, soil active carbon, and soil organic matter. Soil aggregate stability is related to water infiltration and potential for soil erosion, while active carbon serves as an indicator of a readily-available food source for microbial activity, and soil organic matter serves as a mediator for the soil physical, chemical, and biological processes. The sites include: three Purdue Agricultural Centers, two soil and water conservation district sites, 12 farmer sites with conservation cropping systems, and seven conventional comparison sites. The treatments consisted of cover crop versus no cover crop use, or cover crop use with different tillage systems or nitrogen rates. In 2016 and 2017, soil samples were collected at a depth of 0-5 cm, air-dried, and separated into two soil size fractions: 0-2 mm and 2-8 mm. The wet sieve method was used to measure the mean weight diameter of the water stable soil aggregates from the 2-8 mm size fraction in both years. The potassium permanganate method was used to measure the soil active carbon from both size fractions in both years. The dry combustion method was used to measure the soil organic matter from both soil size fractions in 2017 only. Results showed relatively small improvements in soil active carbon and aggregate stability with the addition of three to four years of cover crops to the long-term no-till systems. However, these improvements were greater when comparing the cover crops plus no-till treatments to the conventional-till without cover crops. More work is needed to understand the dynamics of soil aggregate stability, soil active carbon, and soil organic matter in relation to soil health and cover crop use. Cover crops will likely have more impact on soil aggregate stability, active carbon, and organic matter with a longer duration of use.</p><p></p>

Dans un contexte de réchauffement climatique, la fonction « puits » de carbone (C) des tourbières est susceptible de changer en fonction « source » libérant ainsi de grandes quantités de C dans l’atmosphère sous l’effet d’une dégradation accrue de la matière organique (MO). Ainsi cette thèse se sont attachés à étudier la dynamique de dégradation de la MO labile (MOL) et récalcitrante (MOR) en fonction de 3 facteurs contrôlant (le niveau relatif de la nappe, un réchauffement simulé in situ et des variations saisonnières) dans la tourbière ombrotrophe du Forbonnet (25, Jura). Basés sur des analyses biogéochimiques et moléculaires de (i) la tourbe (50cm d’épaisseur), (ii) la fraction organique extractible à l’eau (WEOM) et (iii) les eaux piézométriques, les résultats acquis montrent une dégradation accrue de la MOL (e.g. polysaccharides et produits de son hydrolyse tels que le fructose,le glucose et le saccharose) et de la MOR sous l’effet d’une diminution du niveau de la nappe. Les conditions hydrologiques affectent également les processus de dégradation (sénescence et un éventuel priming effect) et d’humification de la MO pouvant conditionner le piégeage potentiel de laMOL. Après 13 mois d’incubation, l’effet du réchauffement simulé se traduirait par une hausse de l’évapotranspiration dans la condition la plus humide, là où l’étude de la WEOM indique une moindre dégradation de la MOL en surface contrairement aux niveaux profonds. Enfin, les travaux portant sur la dynamique saisonnière du C des eaux piézométriques soulignent le besoin d’intégrer la notion d’interactions entre facteurs contrôlant le cycle du C dans les tourbières pour comprendre leur réponse aux changements climatiques. / In a global warming context, the carbon (C) "sink" function of peatlands may switch to a source function releasing large amounts of C into the atmosphere as a result of an increased decay of organic matter (OM). Thus, these works have focused on the decay dynamics of labile OM and recalcitrant OM (respectively LOM and ROM) according to 3 controlling factors (water-level changes, an in situ simulated warming and seasonally changes) in the “le Forbonnet” bog (25, Jura). Based on biogeochemical and molecular analyses (i) on peat, (ii) on water extractable OM and (iii) on free waters, results suggest an increased decay of LOM (e.g. polysaccharides and its hydrolysis products such as fructose, glucose and sucrose) and MOR under water level changes. Hydrological conditions also affect decay (senescence and an eventual priming effect) and humification processes that can facilitate LOM capture. After 13 months of incubation, simulated warming would lead to an increase of evapotranspiration in the wettest condition where WEOM study indicates a lower LOM decay on the contrary to the deeper peat levels. Studies on the seasonal dynamic of C on free waters underline the need to integrate interactions between factors controlling the C cycle in peatlands to understand their responses to climate change.