Estudou-se o efeito da temperatura na conversão e no coeficiente global de taxa de reação no processo de absorção de SO2 por calcário em reator de leito fluidizado borbulhante atmosférico. O sistema experimental foi constituído por um reator de 160 mm de diâmetro interno e altura de 450 mm e seus periféricos. Os experimentos foram feitos com a introdução de calcário em batelada no leito, fluidizado com ar contendo uma concentração constante e uniforme SO2 e aquecido eletricamente. Utilizou-se granulometria estreita de calcário com diâmetros médios de 545 e 650 &#956m. A areia de quartzo que compunha o leito tinha diâmetro médio de 650 &#956m. Os experimentos foram realizados com bateladas de 50 g de calcário adicionadas ao leito durante o teste, com as demais condições mantidas constantes. As temperaturas utilizadas variaram de 700 a 958°C, a relação entre as velocidades de fluidização e de mínima fluidização foi mantida em 4/1, e fator de fluxo bolha/particulado em torno de 2,6. Os resultados mostraram que a conversão foi relativamente baixa, entre 1,2 e 10,9%, dependendo sobretudo da temperatura utilizada. O coeficiente global de taxa de reação aumentou com a temperatura, atingindo um valor máximo de 500 m/s a 881ºC e decrescendo a partir deste valor. / The effect of temperature in both the conversion and the overall rate of reaction coefficient for the process of SO2 absorption by limestone within a fluidized bed was studied on a bench scale atmospheric bubbling fluidized bed reactor. The reactor had an internal diameter of 160 mm and was 450 mm high. The bed was fluidized with air with a concentration of about 950 ppm of SO2. This mixture was electrically heated. The bed material was quartz sand with a narrow size distribution of around 650 &#956m. Limestone was fed to the bed with narrow sized particles of 545 and 650 &#956m. The experiments were carried out on a batch mode introducing samples of 50 g of limestone into the bed with the other variables kept constant. Process temperatures ranged from 700 to 958°C, the relation between gas fluidization velocity and minimum gas fluidization velocity was fixed at 4/1 and the cross flow factor was around 2.6. The results showed a relatively low conversion of limestone, from 1.2 to 10.9%, depending mostly on temperature. The overall rate of reaction coefficient increased with temperature, reaching a maximum value of 500 m/s at 881°C, and decreasing afterwards.

The application of biotechnologies in the mining sector has intensified over the last 30 years, driven by the increasing demand for metals associated with the rise in energy costs and the awareness for environmentally responsible mining practices. Acidophilic prokaryotes play an important role in biohydrometallurgy, facilitating the solubilisation and recovery of base metals from ores and waste materials. The potential of novel acidophiles of the phylum Firmicutes for applications in biohydrometallurgical processes is examined in this thesis. Eight strains of extremely acidophilic bacteria were studied and shown to belong to the proposed novel genus “Acidibacillus”. These had been isolated previously from several distinct global locations and were shown to be obligately heterotrophic bacteria with potential to carry out tasks critical to biomining such as regenerating ferric iron (by catalysing the dissimilatory oxidation of ferrous iron), generating sulfuric acid (by the oxidation of zero-valent sulfur and tetrathionate; two strains only), and removing potentially inhibitory dissolved organic carbon. These isolates also demonstrated the ability to catalyse the dissimilatory reduction of ferric iron in anaerobic conditions. Results obtained during this study provide the basis for future research to assess their potential roles in microbial consortia applied in the bio-processing of metal ores. A novel obligately anaerobic acidophilic Firmicute (strain I2511) isolated from sediment obtained from an abandoned copper mine, was characterised in terms of its phylogeny and physiology. This isolate formed a separated clade within the Firmicutes, and was considered to represent a novel candidate genus. It also displayed a unique set of physiological traits, distinct from currently validated species of acidophilic Firmicutes. The isolate was an obligate anaerobe that grew via zero-valent sulfur (ZVS) respiration, generating H2S over a wide pH range (1.8 - 5.0), and also catalysed the dissimilatory reduction of ferric iron. Strains of acidophilic sulfatereducing bacteria (aSRB), also Firmicutes, were shown to reduce ZVS at pH as low as 3. These aSRB, together with isolate I2511, populated a novel variant of a low pH sulfidogenic bioreactor. The “hybrid sulfidogenic bioreactor” (HSB) operated using both sulfate and ZVS as electron acceptors, and glycerol as electron donor. The bioreactor successfully remediated and recovered zinc from circum-neutral pH mine-impacted waters with distinct chemical composition collected from two abandoned lead/zinc mines in the U.K. The microbial consortium used in this system proved to be robust, in which the HSB generated H2S consistently under a wide pH range (2 – 7). Experiments demonstrated that H2S could also be generated abiotically in a non-inoculated low pH reactor, by the chemical reaction of ZVS and zero-valent iron to form iron sulfide, and the consequent acid dissolution of the latter. Operational costs and the advantages of biogenic and abiotic generation of H2S for recovery of transition metals from mine waters are discussed.

As formas SO2, HSO3- e SO32- em meio aquoso, são espécies de enxofre (IV) que coexistem; suas concentrações no equilíbrio químico dependem do pH do meio. O estudo das oxidações do S(IV) encontrado na atmosfera, resultante de fontes naturais e antropogênicas, é de fundamental importância, pois os produtos formados têm caráter ácido. Como consequência, ocorre a precipitação ácida, com seus efeitos deletérios ao ecossistema. O presente trabalho procura adicionar novas informações às já acumuladas em estudos anteriores. O estudo praticamente se restringe às condições de laboratório, levando em conta as condições ambientais. Em uma projeção futura, a metodologia poderá ser estendida e adaptada para as determinações do S(IV) na natureza. O método analítico proposto para determinar S(IV) na atmosfera, em fase aquosa, é baseado na reação catalítica onde o S(IV) induz a oxidação do Co(II) a Co(III), em tampão HN3/N3- e na presença do Mn++. O principal composto de coordenação, hexaazidocobaltato (III), é consideravelmente estável e apresenta um máximo de absorção em 365nm, com absortividade molar próxima de 3.104 mol-1cm-1L. Com o uso de uma cubeta de quartzo de 1cm de caminho ótico, a faixa de concentração de uso deste método, é de 280 ppb a 3000 ppb (expressa em HSO3-). A equação que descreve a concentração do S(IV) tem um erro menor que 5%. Para a elaboração do método foram feitos ensaios preliminares, a fim de otimizar as condições experimentais. Os principais parâmetros estabelecidos foram: ordem de adição dos reagentes, tempo de espera para a adição dos outros reagentes, concentração das espécies envolvidas e a solução de referência mais adequada para a leitura espectrofotométrica. As medições foram geralmente feitas a 20°C e 60% de umidade relativa do ar. Também foram realizados estudos em temperatura acima e abaixo de 20°C. A análise das diferentes condições das reações estudadas foi feita pela avaliação da evolução da reação no tempo decorrido. Os compostos de S (IV) são instáveis e por isto foi necessário selecionar uma substância que fosse capaz de coletá-lo no meio ambiente, estabilizá-lo até o momento da reação e que não interferisse na formação do complexo em questão. Com estas finalidades foram estudadas as soluções de MEA, TRIS, NH3 e formaldeído. A reação proposta é catalisada pelo Mn(II), por isto foram feitos estudos visando encontrar o compromisso da concentração deste cátion com o desenvolvimento da reação. O cobalto (II) e o azoteto (N3-) estão em excesso com relação ao S(IV), pela estequiometria da reação. Foi feito um estudo relacionando à concentração de Co(II), N3- e de Mn(II) . Cobalto e manganês são elementos químicos de transição, assim como molibdênio e níquel. Portanto, os dois últimos metais, têm potencialidade de atuar como catalisador ou mesmo formar complexos que absorvam, em substituição ao cobalto. No caso do molibdênio, este, em uma reação competitiva, retira peróxidos da solução que podem oxidar o sulfito. Cobre e ferro interferem no método. Porém, como formam complexos com bandas de absorção máxima, distintas entre si e diferentes de 365nm, foi verificada a possibilidade de determinação das concentrações de S(IV), Cu(II) e Fe(III), em água de chuva, pelo princípio da aditividade. Uma vez que o oxigênio toma parte na reação, foi feito um estudo da possibilidade de utilização do etanol como solvente. Neste solvente, a solubilidade do oxigênio é aproximadamente 20 vezes maior do que na água. O sulfato é um produto da reação e a adição de sulfato de sódio foi estudada, pois o equilíbrio químico é deslocado no sentido de inibir a reação. Finalmente, como a luz pode interferir na reação foi verificada a sua influência no comportamento da mesma. / The proposed analytical method for determining S(IV) in the atmosphere, in aqueous medium, is based upon the catalytic reaction where S(IV) promotes the oxidation of Co(II) to Co(III) in a HN3/N3- - buffer and Mn(II) ions are the catalyst. The main coordination compound is hexaazidecobaltate (III) ([Co(N3)6]3-). This species is relatively stable, it shows an absorption maximum at 365 nm and ε near to 3 x 104 mol-1cm-1L. The concentration range of use for this method is from 280 to 3000 ppb (expressed in HSO3-). Preliminary assays were done for optimizing the experimental conditions. The main parameters established were: order of the added reagents, elapsed time until the addition of the other reagent, concentration of the involved species and the best reference solution for spectrophotometric reading. The measurements were carried out at 20°C and 60% relative humidity. Measurements were also done above and below 20°C. S (IV) compounds are unstable, so it was necessary to select a substance which was able to collect them in the environment, stabilize them until the determination and was not an interferent in the complex formed. For this purpose, solutions for MEA, TRIS, NH4OH and formaldehyde were studied. Copper and iron interfere but they form complexes with different absorption maxima. It was possible to determine the concentrations of S(IV), Cu(II) and Fe(III) in rain water Oxygen takes part in the reaction and the use of ethanol, which dissolves 20 times more oxygen than water, was studied. Finally, as sulphate is a reaction product, sodium sulphate addition was studied too, since the equilibrium is shifted towards reaction inhibition.

Ces dernières années, des problèmes de fonctionnement dus à la formation de dépôts de soufre élémentaire ont été rapportés dans les réseaux de transport du gaz naturel. La compréhension du phénomène passe par la connaissance de la solubilité du soufre dans ces conditions de pression et de température. Des données sont disponibles seulement dans les conditions de gisement du gaz naturel. Un appareillage expérimental a donc été conçu pour mesurer la solubilité du soufre dans les conditions de transport du gaz naturel. Le protocole de mesure se décompose en trois étapes. La première consiste saturer un gaz en soufre dans une cellule d’équilibre. Une fois l’équilibre solide/gaz établi, le gaz saturé est évacué et bulle dans une solution de piégeage qui capture le soufre dissout par absorption réactive. La dernière étape consiste en la quantification indirecte du soufre présent dans la solution de piégeage par chromatographie en phase gazeuse / Over recent years, many problems of elemental sulphur deposits in natural gas transmission line systems have been notified. These problems occur very often immediately downstream of a pressure reduction facility. In order to prevent the apparition of solid sulphur deposits causing security and maintenance problems it is imperative to determine sulphur solubility in natural gas at pressures and temperatures corresponding to transport conditions. For this work, an original experimental apparatus was designed to measure sulphur solubility in natural gas. The protocol principle is schematically divided into three steps: saturation, trapping and quantification. During the first step solid/gas equilibrium is established between the studied gas and the solid sulphur. Then the saturated gas is evacuated and pass through three separators where sulphur is trapped by reactive absorption. Finally the trapping solution are analyzed by gas chromatography to determine the solubility.

O processo de clarificação do caldo de cana-de-açúcar tem sido alvo de vários trabalhos de pesquisa, no intuito de melhorar a qualidade do açúcar obtido, tanto do ponto de vista de novas tecnologias em equipamentos e processos, quanto a respeito do estudo das propriedades físico-químicas da sacarose durante sua decomposição na clarificação. Os POA (Processos Oxidativos Avançados) têm sido aplicados, em especial, ozonização do caldo, tal qual este projeto propõe estudar uma alternativa ao processo convencional de sulfitação do caldo para a obtenção do açúcar cristal branco, através da utilização do peróxido de hidrogênio como agente de redução de cor ICUMSA do caldo e o impacto na degradação da sacarose em compostos não-cristalizáveis, reduzindo o rendimento industrial. Não há relatos na literatura sobre condições ideais de uso do peróxido de hidrogênio, bem como quais alterações essa tecnologia pode ocasionar no caldo. Por isso, buscaram-se elucidar quais são as melhores condições de trabalho e quais fatores influenciam na sua ação, bem como quais são os seus efeitos sobre o caldo tratado. As melhores condições para o uso do peróxido de hidrogênio são: pH entre 3,0 e 7,0, temperatura entre 40 a 70ºC, peróxido de hidrogênio maior que 600 ppm e dextrana menor que 750 ppm. Pode-se verificar que a maturidade da cana-de-açúcar no corte pode influenciar na ação do peróxido de hidrogênio, uma vez que quanto maior o grau de maturação da cana-de-açúcar, maior quantidade de compostos fenólicos e maior a cor inicial do caldo. A cinética de degradação da cor ICUMSA não apresentou distribuição regular, oscilando em pequenos intervalos de tempo, devido provavelmente à pequena quantidade de peróxido de hidrogênio utilizada nos ensaios. Não houve diminuição visual da cor do caldo quando utilizado doses até 5.000 ppm de H2O2. Com relação à turbidez, não foi possível identificar a influência da peroxidação nos valores. Houve degradação de sacarose quando foi feito o tratamento combinando temperatura elevada (62ºC) com pH ácido (3,8). A rede neural artificial (RNA) mostrou um bom ajuste na maioria dos casos apresentados e indicou a variável temperatura como a que apresentou maior influência na diminuição da absorbância à 420 nm. A segunda variável com maior influência foi o Brix do caldo de cana-de-açúcar. A espectrometria de massa mostrou que a peroxidação, nas condições reacionais avaliadas, não foi capaz de reduzir significativamente a cor do caldo, sugerindo que haja uma promoção de sedimentação de algumas impurezas do caldo, o que faz com que haja uma diminuição visual da cor do mesmo, não ocorrendo aparentemente reação química no caldo, quando utilizamos doses de 50.000 ppm. Assim o peróxido de hidrogênio não funcionou como um agente clarificante, nas condições estudadas. / The process of sugarcane juice clarification has been the subject of several research papers in order to improve the quality of sugar obtained both from the point of view of new technologies in equipment and processes , as concerning the study of physico- chemical properties of sucrose during decomposition in clarification . The AOP \'s (Advanced Oxidation Process ) have been applied in particular ozonation of the juice as such this design proposed to study an alternative to conventional process sulphiting of the juice to obtain sugar white crystal through the use of hydrogen peroxide as reduction ICUMSA color of juice and the impact on the degradation of sucrose into non- crystallizable compounds by reducing industrial productivity agent. There are no reports in the literature on optimal conditions of use of hydrogen peroxide as well as the technology changes which may result in the juice. Therefore , we sought to elucidate what are the best working conditions and factors which influence in its action, and what are its effects on the treated juice. The best conditions for the use of hydrogen peroxide are: pH lower than 7.0 or higher than 3.0, temperature greater than 40 °C and below 70 °C, hydrogen peroxide greater than 600 ppm and lower than 750 ppm dextran. We observed that the maturity of the sugarcane cutting can influence the action of hydrogen peroxide, since the more mature sugarcane, a greater number of phenolic compounds are produced and the higher the initial color of the juice. The kinetics of ICUMSA color degradation showed no regular distribution, oscillating at short time intervals, probably due to the small amount of hydrogen peroxide used in the tests. There was no visual color decrease of the juice. Regarding turbidity, it was not possible to identify the influence of peroxidation values . There was sucrose degradation when the treatment was made by combining high temperature (62°C) at acid pH (3.8). The artificial neural network (ANN) showed a good fit in most cases presented and indicated the variable temperature with the highest influence on the absorbance decrease at 420 nm. The second variable with the greatest influence was the Brix of sugarcane juice. Mass spectrometry showed that peroxidation in the reaction conditions evaluated was not able to significantly reduce the sugarcane juice color, suggesting a promotion of sedimentation of some impurities in the juice, hindering a reduction of its visual color, and apparently, there was no chemical reaction in the juice, using rate of hydrogen peroxide of 50,000 ppm. Thus hydrogen peroxide did not work as a clarifying agent, in the studied conditions

A preocupação com a disposição de lodo de esgoto no Brasil resultou do aumento do volume de esgoto tratado e tem exigido alternativas para a sua disposição final. A princípio, a utilização agrícola se apresenta como uma das propostas viáveis uma vez que o lodo é rico em matéria orgânica, macro e micronutrientes necessários à fertilidade dos solos. Entretanto, há que ser considerado o impacto ambiental de alguns desses elementos, como Hg, As, Cd, Pb, Ag, Cu, Zn entre outros, sobre o solo, biota e águas, superficiais e subterrâneas. A ETE Barueri é a maior estação de tratamento de esgoto do estado de São Paulo e recebe efluentes domésticos e industriais, motivo pelo qual os metais pesados são encontrados nos lodos em teores muitas vezes acima dos permitidos pela legislação federal (CONAMA, 2006). Com base nesses aspectos esta tese investigou principalmente a variação dos teores dos elementos Zn, Ni, Cr, Cu e Fe em 30 amostras de lodo, coletadas nos períodos chuvoso e seco, por um ano, para verificar: a influência da sazonalidade na sua qualidade para fins agrícolas, as suas possíveis associações com outros elementos e frações químicas na matriz do lodo (íons trocáveis, matéria orgânica, ácidos húmicos e fúlvicos, carbonatos, oxi-hidróxidos de ferro e manganês), bem como a capacidade de adsorção desses metais pela turfa, como proposta de tratamento. Os métodos utilizados para essa pesquisa incluíram as análises químicas por ICPOES e fluorescência de raios X (FRX) e seu tratamento estatístico, o fracionamento químico, a espectroscopia de infravermelho (FTIR), a microscopia eletrônica de varredura (MEVEDS), a difração de raios X (DRX), a análise térmica e a determinação da razão isotópica d34S. Estas quatro últimas técnicas foram empregadas, em especial, para averiguar a procedência do enxofre contido no lodo. Os ensaios de adsorção com a turfa foram efetuados por batelada. Os resultados obtidos revelaram que os teores de muitos dos elementos químicos existentes no lodo de esgoto variaram em função das precipitações pluviométricas, dentre eles o níquel, o zinco e o enxofre, muitas vezes encontrando-se acima dos valores permitidos pela legislação. Verificou-se também que os maiores percentuais dos metais analisados no lodo de esgoto encontravam-se associados à fração dos \"oxi-hidróxidos de ferro mal cristalizados\" e não à matéria orgânica, constituinte bastante relevante da sua matriz. Na fração matéria orgânica, o teor de cobre foi o mais elevado dentre os demais elementos. Os espectros FTIR indicaram o baixo grau de humificação dessa matéria orgânica. As fezes humanas, os surfactantes e os combustíveis fósseis apareceram como provável origem do enxofre no lodo. A solução \"água de chuva\" extraiu níquel e cobre do lodo de esgoto nos ensaios em batelada e a turfa adsorveu preferencialmente o níquel ao cobre. Os percentuais de Zn e Ni associados aos ácidos húmicos e fúlvicos retidos pela turfa foram maiores em pH 6,5 que em pH 8,5. O cobre apresentou comportamento contrário. Os resultados obtidos permitem afirmar que qualquer emprego a ser dado a esse tipo de lodo exige tratamento prévio. / The increase of the wastewater treated volume in Brazil has demanded alternatives to the sewage sludge final disposal. At first, agricultural use is one of the viable recommendations since sludge is rich in organic matter, macro and micronutrients necessary to the fertility of the soil. However, it is necessary to consider the environmental impact of some of these elements such as Hg, As, Cd, Pb, Ag, Cu, Zn among others, on the soil, biota and surface and subterranean water. ETE Barueri is the biggest treatment plant in the state of São Paulo and receives domestic and industrial effluents and for this reason heavy metals are found in the sludge in contents highly above those allowed by federal Brazilian legislation (CONAMA, 2006). Based on these aspects this study mainly investigated the fluctuation in the concentration of the elements Zn, Ni, Cr, Cu and Fe in 30 samples of sludge, collected in the rainy and dry periods, over a year, in order to check: the influence of seasonality on its quality for agricultural purposes; their possible associations with other elements and its distribution in the solid phase in the sludge matrix (exchangeable ions fraction, organic matter fraction, humic and fulvic acids fraction, carbonates fraction, iron and manganese oxihydroxides fraction) as well as the adsorption capability of these metals by the peat, as a recommendation for treatment. The methods used for this research included the chemical analysis by ICP-OES and X-ray fluorescence (FRX), their statistical analysis, the chemical fractionation, the infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive scan (EDS), the X-ray diffraction (XRD), the thermal analysis and the isotopic ratios analysis ?34S. The last four techniques were used, specially, to investigate the origin of the sulphur present in the sludge. The adsorption experiments with the peat were conducted in bulk. The obtained results showed that the concentrations of several of the chemical elements present in the sewage sludge, among them nickel, zinc and sulphur, varied in relation to the pluvial precipitations, often being above values allowed by legislation. It was also found that the greater percentages of the metals in the sewage sludge were associated with the fraction of the poorly crystallised iron oxihydroxides and not with the organic matter, a rather relevant component of its matrix. In the organic matter fraction, the amount of copper was the highest amongst the other elements. The FTIR spectrums indicated the low decomposition degree of that organic matter. Human feces, surfactants and fossil fuels appeared as probable origin of the sulphur in the sludge. The \"rainwater solution\" extracted nickel and copper from the sewage sludge in the experiments in bulk, and the peat adsorbed the nickel preferably to the copper. The percentages of Zn and Ni, associated with the humic and fulvic acids, retained by the peat, were higher in pH 6,5 than in pH 8,5. The copper had the opposite behaviour. The results obtained allow us to state that any utilization of this type of sludge requires previous treatment.

O presente trabalho apresenta uma alternativa ao processo de classificação do defeito da segregação central em amostras de aço, utilizando as imagens digitais que são geradas durante o ensaio de Baumann. O algoritmo proposto tem como objetivo agregar as técnicas de processamento digital de imagens e o conhecimento dos especialistas sobre o defeito da segregação central, visando a classificação do defeito de referência. O algoritmo implementado inclui a identificação e a segmentação da linha segregada por meio da aplicação da transformada de Hough e limiar adaptativo. Adicionalmente, o algoritmo apresenta uma proposta para o mapeamento dos atributos da segregação central nos diferentes graus de severidade do defeito, em função dos critérios de continuidade e intensidade. O mapeamento foi realizado por meio da análise das características individuais, como comprimento, largura e área, dos elementos segmentados que compõem a linha segregada. A avaliação do desempenho do algoritmo foi realizada em dois momentos específicos, de acordo com sua fase de implementação. Para a realização da avaliação, foram analisadas 255 imagens de amostras reais, oriundas de duas usinas siderúrgicas, distribuídas nos diferentes graus de severidade. Os resultados da primeira fase de implementação mostram que a identificação da linha segregada apresenta acurácia de 93%. As classificações oriundas do mapeamento realizado para as classes de criticidade do defeito, na segunda fase de implementação, apresentam acurácia de 92% para o critério de continuidade e 68% para o critério de intensidade. / This work presents an alternative to the classification process of centerline segregation in steel samples, using the digital images that are generated during the Baumann test. The proposed algorithm aims to aggregate the digital image processing techniques and experts knowledge on centerline segregation to classify the reference defect. The implemented algorithm includes the identification and segmentation of segregation line, applying the Hough transform and adaptive thresholding. Additionally, the algorithm presents a proposal for mapping the centerline segregation attributes on the different defect degrees of severity, according to the intensity and continuity criteria. The mapping was carried out by analyzing the individual characteristics such as length, width and area of the segmented elements that make up the segregation line. The evaluation of the algorithm performance was done in two specific moments, according to implementation phase. In carrying out this evaluation, 255 images of real samples from two steel plants were analyzed, distributed in different degrees of severity. The results of the first phase of implementation show that the identification of the segregation line has 93% accuracy. The classification results from the attributes mapping realized to the defect severity degrees in the second implementation phase, has accuracy of 92% for the continuity criteria and 68% for the intensity criteria.

Thesis (Ph.D. (Physics)) -- University of Limpopo, 2018 / Beyond conventional intercalation chemistry, reaction of lithium with sulphur and oxygen (so-called “Li-air” batteries) have the potential to provide 2 to 5 times the energy density of current Li-ion battery systems. However, both Li/S and Li/O2 systems suffer from cycling performance issues that impede their commercial applications: Li/O2 cycling is limited by electrolyte decomposition and large cell polarization; Li/S suffers from the low conductivity of S and the solubility of intermediary polysulfide species during cycling. It has been reported that Se and mixed SexSy represent an attractive new class of cathode materials with promising electrochemical performance in reactions with both Li and Na ions. Notably, unlike existing Li/S batteries that only operate at high temperature, these new Se and Li/SexSy electrodes are capable of room temperature cycling. Initially, stabilities of insoluble discharge products of oxygen and sulphur in the Li-S and Li-O2 batteries were investigated using density functional theory within the generalized gradient approximation, and these were deduced from their structural, electronic and mechanical properties. The structural properties are well reproduced and agree to within 3% with the available experimental data. Li2S, Li2O and Li2O2 and Li2S2 structures all have negative heats of formations indicating that they are stable, however, that of Li2S2 structure was relatively high compared to others. Calculated phonon dispersion and elastic properties revealed that Li2O, Li2S and Li2O2 structures are mechanically stable and great agreement with experimental work. The Li2S2 structure displayed soft modes associated mainly with sulphur atoms vibrations in the a-b plane, hence it is not mechanically stable in agreement with the negative C13. Stable Li2S2 polymorphs were extracted from soft modes of calculated phonon dispersions along the gamma direction in the Brillioun zone. Temperature is known to have a significant impact on the performance, safety, and cycle lifetime of lithium-ion batteries (LiB). In order to explore properties of discharge products associated with Li/S and Li/Se batteries at different temperatures, molecular dynamics and cluster expansion methods were employed. The former was achieved by firstly deriving empirical interatomic potentials of Li2S and Li2Se which were fitted to experimental and DFT calculated data. The potentials were validated against available experimental and calculated structure, elastic properties and phonon spectra. In addition, complex high temperature transformations and melting of Li2S and Li2Se were reproduced, as deduced from molecular dynamics simulations. Both Li2S and Li2Se were found to withstand high temperatures, up to 1250K each which is a desirable in future advanced battery technologies. Furthermore, cluster expansion and Monte-Carlo simulations were employed to determine phase changes and high temperature properties of mixed Li2S-Se. The former generated 42 new stable multi-component Li2S-Se structures and ranked metastable structures by enthalpy of formation. Monte Carlo simulations produced thermodynamic properties of Li2S-Se system for the entire range of Se concentrations obtained from cluster expansion and it demonstrated that Li2S-Se is a phase separating system at 0K but changes to mixed system at approximately 350K which was confirmed by constructed by phase diagram of Li2S-Se system. It was finally demonstrated that molecular dynamics and Monte Carlo simulations techniques yield consistent results on phase separation and high temperature behavior of Li2S-Se at 50% of sulphur and selenium.

Jusqu’à 40% des protéines sont connues pour fixer des métaux, ces hétéroatomes jouant un rôle capital dans la régulation, la catalyse ou le maintien de la structure de ces protéines. Ces métalloprotéines sont ubiquitaires et d’une importance primordiale dans les trois domaines du vivant. Cependant, les méthodes actuelles dédiées à l’identification des membres de cette grande famille dans les protéomes bactériens sont soit inadaptées pour des approches à grande échelle, soit présentent des performances relativement limitées en l’absence d’une structure tridimensionnelle résolue. Dans ce contexte, différents outils d’analyse de séquence ont été testés, en recherchant des descripteurs de ces protéines (e.g. motifs, domaines conservés, empreintes phylogénétiques). Pour pallier le relatif manque de sensibilité de ceux-ci, de nouveaux descripteurs ont été construits, dédiés spécifiquement à l’identification des protéines à centre fer-soufre : (i) des profils de co-conservation des ligands du métal et (ii) des profile-HMMs adaptés à la détection d’homologues distants. Les pouvoirs prédictifs respectifs de ces catégories de descripteurs ont été évalués sur un jeu de protéines fer-soufre expertisé, en les considérant soit séparément soit en combinaison. L’ensemble de ces descripteurs a finalement été intégré dans un modèle linéaire généralisé en utilisant la technique d’elastic-net. Le modèle prédictif obtenu a été évalué sur le protéome complet d’Escherichia coli, sur lequel il atteint une précision de 89% et une sensibilité de 83%. Enfin, il a été appliqué à environ 300 protéomes pour explorer différentes relations biologiques comme l’abondance relative des protéines Fe-S et la tolérance à l’oxygène des organismes auxquelles elles appartiennent. / Up to 40% of all proteins are known to bind metals, the intrinsic metal atoms providing catalytic, regulatory and/or structural roles critical to their functions. These metalloproteins are ubiquitous and of major importance within the three domains of life. However, current methods dedicated to identifying members of this large family within bacterial proteomes are either not suitable for large-scale approach or are of relatively limited performance when no 3D structural template is available. Within this context, different sequence analysis tools relying on different category of protein descriptors (e.g. patterns, conserved domains, phylogenetic prints) were assessed. To overcome their relative lack of sensibility, new descriptors, specific towards iron-sulfur proteins identification were built: (i) co-conservation profiles of the metal ligands and (ii) tailored profile-HMMs for remote homologs detection. Their respective predictive power towards the identification of a manually curated iron-sulfur proteins dataset were assessed, either separately or in combination. All relevant descriptors were finally gathered into a generalized linear model by using the elastic-net method. The predictive model has been evaluated on Escherichia coli whole proteome resulting in a precision of 89% and a recall of 83%. Eventually, it has been applied to 300 proteomes allowing investigating different biological relationships, such as iron-sulfur proteins relative abundances and the oxygen dependency of bacterial organisms.

Multi-services cover crops (MSCC) grown during fallow period between two cash crops provide various ecosystem services. Among species used as MSCC, crucifers can efficiently prevent nitrate and sulphate leaching by catching residual soil mineral nitrogen (N) and sulphur (S) afterthe preceding cash crop (N and S catch crop services). Crucifers also have a unique capacity to suppress pathogens due to the biocidal hydrolysis products of endogenous secondary metabolites called glucosinolates (GSL). The aim of our study was to assess the provision of various ecosystem services linked to N, S cycles and biocontrol potential for a wide range of bispecific crucifer-legume mixtures in comparison to sole cover crops of legume and crucifer. We carried out experiments in 2 contrasted sites (Toulouse and Orléans regions, France) during 2 years in order to assess these services and the compatibility of various bi-specific crucifer-legume mixtures. We tested a great diversity of species, such as i) crucifers : rape, white mustard, Indian mustard, Ethiopian mustard, turnip, turnip rape, radish and rocket, and ii) legumes: Egyptian clover, crimson clover, common vetch, purple vetch, hairy vetch, pea, soya bean, faba bean, and white lupin. Our study demonstrated that crucifer-legume mixtures can provide and mutualize various ecosystem services by reaching from 2 thirds (GSL production, S and N green manure) to the same level ofservice (N and S catch crop) than the best sole family of species. GSL profile and concentration did not change in mixtures meaning that crucifer-pests interactions were identical. Through a literature review we also illustrated that biocontrol services of crucifers could be largely maintained in crucifer-legume mixtures for a wide range of pathogens and weeds while reducing potential disservices on beneficials and increasing N related service