Os manguezais são ambientes de transição entre os ecossistemas terrestres e marinhos, essenciais para o crescimento e o desenvolvimento de muitas espécies de elevado interesse ecológico e econômico. Apesar de ter sua importância reconhecida, são constantemente impactados por diversos poluentes que influenciam sua estabilidade. Estes ecossistemas caracterizam-se por serem anaeróbicos, ricos em sulfato e em matéria orgânica, sendo os microrganismos fundamentais na ciclagem de nutrientes, em especial os envolvidos no ciclo do enxofre, onde os procariotos redutores de sulfato (sulphate-reducing prokaryotes, SRP) aparecem como um grupo frequente e com um papel preponderante. O presente estudo mostrou que as comunidades de arquéias, bactérias e bactérias redutoras de sulfato (sulphatereducing bacteria SRB) são abundantes, diversas e responsivas aos estados de intervenção dos manguezais. A abundância medida por qPCR mostrou que as quantidades de arquéias e bactérias aumentam com a contaminação. A diversidade estudada por pirosequenciamento do gene ribossomal 16S DNAr indicou que estes grupos são diversos, mostrando filos Euryarcheota e Crenarcheota do domínio Archaea, e os filos Deltaproteobacteria e Gammaproteobacteria, do domínio Bacteria, como grupos frequentes. A estrutura destas comunidades, avaliada por análises de co-ocorrência, revelou que a microbiota responde à contaminação, diminuindo e simplificando as interações, quanto maior for a contaminação. A diversidade dos grupos relacionados ao ciclo do enxofre, estudada por DGGE (aprA e dsrB), pirosequenciamento (dsrB) e GeoChip (aprA, dsrB), mostrou que a classe Deltaproteobacteria, representada pelas ordens Desulfobacterales e Desulfovibrionales, é o grupo prevalente na redução do sulfato, e as classes Gammaproteobacteria e Betaproteobacteria devem atuar na oxidação do enxofre (sulphur-oxidising - SOB). O GeoChip (aprA, dsrB) foi a única metodologia que permitiu detectar arquéias redutoras de sulfato (gêneros Archaeoglobus e Pyrobaculum), sendo esta a primeira descrição de tais organismos em ecossistemas de manguezais. Desse modo, estes resultados evidenciam que a microbiota em áreas de manguezais responde à contaminação, tendo uma alta frequência de SRB e SOB, ressaltando, assim, a importância do ciclo do enxofre em ambientes de manguezais. / Mangroves are transitional environments between terrestrial and marine ecosystems, essential for the growth and development of many species with high ecological and economical interests. Despite its recognized importance, mangroves are constantly impacted by various pollutants, affecting its stability. These ecosystems are characterized as anaerobic, rich in sulfate and organic matter, where the microorganisms are essential to the nutrient cycling, particularly those involved in the sulfur cycle, where sulphate-reducing prokaryotes (SRP) appear as frequent and taking an important role. The present study showed that communities of archaea, bacteria and sulphate reducing bacteria (SRB) are abundant, diverse and responsive to state intervention of the mangrove. The abundance measured by qPCR showed that the quantities of archaea and bacteria increase with the contamination. The diversity studied by pyrosequencing of the 16S rDNA ribosomal gene indicated that these groups are diverse, showing Euryarcheota and Crenarcheota phyla of the domain Archaea, and Deltaproteobacteria and Gammaproteobacteria classes of the domain Bacteria, as the most frequent groups. The structure of these communities, as assessed by analysis of network, revealed that the microbiota responds to contamination, reducing and simplifying interactions in the higher contamination. The diversity of groups related with the sulfur cycle studied by DGGE (aprA and dsrB), pyrosequencing (dsrB) and GeoChip (aprA, dsrB) showed that Deltaproteobacteria, represented by orders Desulfobacterales and Desulfovibrionales, is a prevalent group in the sulfate reduction, while Gammaproteobacteria and Betaproteobacteria are frequent in the sulfur oxidation (sulfur-oxidising bacteria - SOB). The GeoChip (aprA, dsrB) was the only method that allowed to detect sulfate-reducing archaea (genera Archaeoglobus and Pyrobaculum), which is the first description of these organism on mangrove ecosystems. Thus, these results show that the microbiota in mangroves areas responds to contamination, having a high frequency of SRB and SOB, thus highlighting the importance of the sulfur cycle in mangrove environments.

Bifenilas policloradas (PCBs) são compostos de difícil degradação presentes na composição de ascarel, muito utilizado como fluidos dielétricos e isolantes. Neste contexto, a presente pesquisa teve como objetivo avaliar a diversidade de microrganismos em biofilmes de reatores anaeróbios na presença de PCB empregando Métodos de Microbiologia de Anaeróbios Estritos e de Biologia Molecular. Em reator anaeróbio horizontal de leito fixo (RAHLF), alimentado com etanol, formiato, Triton X-100 (0,1%) e ascarel (1 mL/L), operado com tempo de detenção hidráulica (TDH) de 24 horas, foi retirado a comunidade microbiana do biofilme da espuma de poliuretano. Os grupos microbianos encontrados por meio da clonagem e sequenciamento do gene RNAr 16S para o domínio Bacteria foram relacionados aos filos Thermogae, Proteobacteria (Brachymonas petroleovorans, 100% de similaridade e Methylobacillus, 98% de similaridade), Firmicutes (Clostridium, 97% de similaridade, Syntrophomonas, 100% de similaridade e Sporomusa com 100% de similaridade), Synegistetes (Synergistes, 98% de similaridade), Spirochaetes (Leptonema illini, 98% de similaridade), Aminanaerobia, Deferribacteres, Chlorobi, Chloroflexi e Armatimonadetes. Além disso, como nesse biofilme foram identificadas bactérias redutoras de ferro, procedeu-se a sua quantificação por meio da técnica de tubos múltiplos (NMP, Número Mais Provável) obtendo 5,26 x \'10 POT.12\' NMP/g STV de bactérias redutoras de ferro. Ensaio em batelada foi realizado separadamente sob duas condições: (1) metanogênica e (2) ferro redutora. Em ambas as condições foram adicionadas aroclor 1260 (PCB). Os reatores, sob condição metanogênica, foram alimentados com meio de cultivo Angelidaki e substratos orgânicos (formiato e etanol), além de aroclor 1260 (0,2 \'mü\'g/L). Para simular a condição redutora de ferro foi acrescido ao meio de cultura Angelidaki, EDTA férrico (1,86 g/L). A produção de metano, na presença de aroclor 1260 foi de 3,8 x \'10 POT.-4\' mmol \'CH IND.4\'/g STV. A presença de bactérias ferro redutoras foi confirmada indiretamente pela taxa média de redução férrica (90%) nos reatores em batelada, após 60 dias de operação. Por meio de PCR/DGGE, elaborou-se um dendograma das amostras deste ensaio em batelada (metanogênico e redutor de ferro) comparativamente com as do reator RAHLF (biofilme presente na parede do reator e no material suporte). Os reatores em batelada apresentaram similaridade entre si de 79% e 92% para os domínios Bacteria e Archaea, respectivamente. As amostras do reator RAHLF foram 80% (Bacteria) e 96% (Archaea) similares. A existência de bactérias degradadoras de PCB, bem como, bactérias redutoras de ferro no biofilme anaeróbio contribuiu com informações sobre o consórcio microbiano e sua diversidade. / Polychlorinated biphenyls (PCBs) are compounds of difficult degradation, a component of askarel, which were used widely as coolants and lubricants. Hence, this study evaluated the diversity of microorganisms in the presence of PCBs in anaerobic reactors. For such, methods as Strict Anaerobic Microbiology and Molecular Biology were employed. The microbial community of the biofilm, developed in a fixed horizontal bed anaerobic reactor (RAHLF), was studied using the technique of cloning and sequencing of RNAr 16S gene for the Bacteria domain. The reactor had immobilized cells in polyurethane foam with ethanol and formate as a carbon source, Triton X-100 (0.1%) and polychlorinated biphenyls (1 mL/L), and operated with 24 hours HRT. The microbial groups found in this biofilm were related to phyla Thermogae, Proteobacteria (Brachymonas petroleovorans, 100% similarity and Methylobacillus, 98% similarity), Firmicutes (Clostridium, 97% similarity Syntrophomonas, and 100% similarity with Sporomusa 100% similarity), Synegistetes (Synergistes, 98% similarity), Spirochaetes (Leptonema Illini, 98% similarity), Aminanaerobia, Deferribacteres, Chlorobi, Chloroflexi and Armatimonadetes. Furthermore, as bacteria that reduce iron were found, we proceeded the quantification by the multiple tube method (MPN) for this group, obtaining 5.26 x \'10 POT.12\' MPN/g STV of iron-reducing bacteria. The batch reactors evaluated the growth of microorganisms in two condictions: (1) methanogenic e (2) iron reduction, both had the presence of PCBs (Aroclor 1260). The reactor, under methanogenic condition, was fed with synthetic substrate Angelidaki, ethanol and formate, used as carbon source, and aroclor 1260 (0.2 \'mü\'g /L). To simulate the condition of iron reducing, the same synthetic substrate was supplemented with ferric EDTA (1.86 g/L). The production of methane in the presence of aroclor 1260, was 3.8 x \'10 POT.-4\' mmol \'CH IND.4\'/g STV. The presence of iron reducing bacteria, after 60 days, was confirmed indirectly by the average rate of iron ferric reduction (90%). Filogenetics analysis (PCR/DGGE) compared the samples of this batch reactor - methanogenic and reduction of iron ferric -, with the samples of RAHLF - the biofilm in the reactor wall and the support material. The two condictions in batch reactors showed similarity of 79% and 92% respectively for the Bacteria and Archaea domain. Therefore, both samples of RAHLF showed 80% (Bacteria) and 96% (Archaea) of similarity. In other words, more similarity were presented due configuration of the reactor as well as the type of PCB added. As a result, the existence of PCBs degrading bacteria and iron-reducing bacteria in anaerobic biofilm, provided informations about the microbial consortium and its diversity in the presence of PCB.

Neste trabalho foram realizadas sínteses do nitrosilo complexo trinuclear de rutênio de fórmula [Ru3O(CH3COO)6(NO)(py)2]PF6 (py = piridina) seguindo duas rotas sintéticas diferentes (convencional (a) e uma nova (b) ) a fim de verificar e comparar a eficiência de ambas. Além disso, foi feito o mapeamento da rota sintética convencional para analisar a melhor forma de conduzi-la em cada etapa para que a síntese fosse bem sucedida. Com isso, foi possível afirmar na rota (a) que é preciso purificar dois precursores: o precursor 1 [Ru3O(CH3COO)6(S)3]+ e 3 [Ru3O(CH3COO)6(CO)(L)2], não sendo necessário a purificação do produto final. As modificações vistas necessárias para a otimização da síntese (a) foram a utilização de uma solução recém preparada de bromo e a substituição do metanol seco no frasco lavador por diclorometano seco. Não se descarta a possibilidade da nova rota sintética (b), somada às modificações apontadas neste trabalho, apresentar bons resultados. As caracterizações foram feitas utilizando técnicas de espectroscopia na região UV-visível, infravermelho e RMN. Os estudos de reatividade mostraram que, para ambos os complexos analisados ([RuIII,III,III3O(CH3COO)6(NO)(py)2]PF6 e [RuIII,III,III3O(CH3COO)6(4-acpy)2(NO)]PF6), sugere-se a formação da espécie [RuIII,III,II3O(CH3COO)6(NO2-)(L)2]- onde L = 4-acpy ou py - sendo esta reação dependente da concentração de íons hidroxila do meio. Estudos da reatividade e redução do [Ru3O(CH3COO)6(NO)(py)2]PF6 com o redutor de interesse biológico ácido ascórbico na presença de íons OH-, permitiram sugerir uma hipótese para o mecanismo de liberação de NO0 com estímulo redox, na ausência de luz. Propõe-se que primeiramente o ligante NO0 coordenado sofra um ataque nucleofílico dos íons hidroxila presentes no meio, concomitante a uma transferência eletrônica intra-molecular que gera a espécie [RuIII,III,II3O(CH3COO)6(NO2-)(py)2]-. Este último é reduzido pelo ácido ascórbico, restaurando o ligante NO0 que, agora coordenado à unidade metálica reduzida [RuIII,III,II3O], finalmente é labilizado, gerando o complexo [Ru3O(CH3COO)6(S)(py)2]0 / In this work, the synthesis of the trinuclear ruthenium complex [Ru3O(CH3COO)6(NO)(py)2]PF6 (py = pyridine) was performed following two different synthetic routes (conventional (a) and a new one (b)) in order to verify and to compare the efficiency of both. In addition, the mapping of the conventional synthetic route was done to analyze the best way to conduct it at each step for the synthesis to be successful. It was possible to state in route (a) that two precursors must be purified: precursor 1 [Ru3O(CH3COO)6(S)3]+ and 3 [Ru3O(CH3COO)6(CO)(L)2], no purification of the final product being necessary. The modifications required for the optimization of synthesis (a) were the use of a freshly prepared solution of bromine and the substitution of the dry methanol in the washing flask by dry dichloromethane. We can not rule out the possibility of the new synthetic route (b), added to the modifications pointed out in this work, to present good results. The characterizations were made using UV-visible, infrared and NMR spectroscopy techniques. Reactivity studies for both complexes analyzed ([RuIII,III,III3O(CH3COO)6(NO)(py)2]PF6 and [RuIII,III,III3O(CH3COO)6(4-acpy)NO)]PF6), suggested the formation of the species [RuIII,III,II3O(CH3COO)6(NO2-)(L)2]- - where L = 4-acpy or py - this reaction being dependent on the concentration of hydroxyl ions in the medium. Studies of the reactivity and reduction of compound [Ru3O(CH3COO)6(NO)(py)2]PF6 with the biological reductant ascorbic acid, in the presence of OH- ions, allowed to suggest a hypothesis for the NO0 release mechanism with redox stimulus, in the absence of light. It is proposed that the coordinated NO0 ligand undergoes a nucleophilic attack of the hydroxyl ions present in the medium, concomitant to an intra-molecular electron transfer that generates the species [RuIII,III,II3O(CH3COO)6(NO2-)(py)2]-. The latter is reduced by ascorbic acid, restoring the ligand NO0 which, now coordinated to the reduced metal unit [RuIII,III,II3O], is finally labilized, generating the complex [Ru3O(CH3COO)6(S)(py)2]0

Photovoltaic (PV) system is one of the most prominent energy sources, producing electricity directly from sunlight. In additionally, it is easy to install and is supported financially by many governments as part of their strategy to reduce CO2 gas emissions, and to achieve their agreed set of reduction targets by 2020. In the meantime, researchers have been working on the PV system to make it more efficient, easy to maintain, reliable to use and cost effective. In the stand-alone PV system, a battery is required. This is due to the fluctuating nature of the output energy delivered by the PV arrays owing to the weather conditions and the unpredictable behaviour of uses with regard to the consumption of energy. During the hours of sunshine, the PV system is directly feeding the load and any surplus electrical energy is stored in the battery at a constant current. During the night, or during a period of low solar irradiation, the energy is supplied to the load from the battery. However, the stand-alone PV system is designed to provide an acceptable balance between reliability and cost, which is a major challenge to the designer owing to the approaches used to size the PV arrays and the battery bank. As a result, the unpredictable, quick daily changes on the PV output is not dependable. Moreover, battery performance, length of life and energy efficiency depends on the rate at which it is discharged. Therefore, it is essential to use other methods to deal with any quick variation in energy. In this thesis, a super capacitor is used to solve this problem, as it can deal with the fast-changing weather, or a rapid variation in the energy requirements of the customer. A critical evaluation with in-depth analysis of the placement and the implementation for the super-capacitor in the PV standalone system has been carried out. The results show, super-capacitor capacitance and the converter efficiency affect the delivered load energy. However, the bi-directional topology performs better than uni-directional under the same conditions. Finally, a further improvement of the system at component level, has been developed through an energy recovery snubber for the switching transition and achieved a recovery of energy for the resistive load, 94.44% for the turn on transition and 92.86% for the turn off transition. Moreover, for the inductive load, 78.33% and 97.33% of energy has been recovered for the turn on and for the turn off transition respectively.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Bactérias redutoras de sulfato (BRS) possuem um papel importante na corrosão de ligas metálicas expostas em hábitats marinhos, óleos e solos úmidos. A redução do sulfato por estas bactérias resulta na produção de H2S, podendo influenciar os processos anódico e catódico na corrosão de materiais. Neste trabalho, o comportamento da corrosão microbiológica no aço carbono AISI 1020 foi avaliada em meio Postgate C, na presença e na ausência de BRS, as quais foram isoladas da camada de ferrugem presente numa tubulação submersa da Baía de Guanabara RJ. A taxa de corrosão e o comportamento eletroquímico do aço nas duas condições foram investigados através dos métodos de perda de massa e de polarização potenciodinâmica. A formação do biofilme e dos produtos de corrosão na superfície do aço foram observados por microscopia eletrônica de varredura (MEV) e por espectroscopia de energia dispersiva (EDS). Em complementação, foi realizada a quantificação das BRS (planctônicas e sésseis) pelo método do número mais provável (NMP). A presença de BRS no meio ocasionou o deslocamento do potencial de corrosão para valores mais negativos em todos os tempos de ensaio estudados, indicando um aumento no processo corrosivo. Nos ensaios de perda de massa, a taxa de corrosão do aço carbono foi maior na ausência de BRS, provavelmente devido à formação de um biofilme na superfície do metal nos ensaios com inóculo, e a uma menor tendência de haver corrosão generalizada neste tipo de meio. As micrografias de MEV revelaram a presença de agregado celular na superfície do aço carbono durante o experimento, e a presença de pites profundos após remoção do biofilme, mostrando prevalência deste tipo de corrosão. Com 35 dias de ensaio, a densidade de corrente de corrosão aumentou na presença de BRS / Sulfate-reducing bacteria (SRB) play an important role in the corrosion of alloys exposed in marine habitats, wet soils and oils. The sulfate reduction by these bacteria results in production of H2S, which may influence processes in the anodic and cathodic corrosion of materials. In this work, the behavior of microbial corrosion in carbon steel AISI 1020 was evaluated in Postgate C medium, in the presence and absence of SRB, which were isolated from a layer of rust on a pipeline submerged in Guanabara Bay - Rio de Janeiro. The corrosion rate and the electrochemical behavior of steel in the two conditions were investigated by weight loss and potentiodynamic polarization methods. Biofilm formation and corrosion products on the steel surface were observed by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). In addition, the quantification of BRS (planktonic and sessile) was carried out by the most probable number method (MPN). The presence of SRB in the medium caused the shift of corrosion potential to more negative values in all experimental times studied, indicating an increase in corrosion. In the weight loss tests, the corrosion rate was higher in the absence of BRS, probably due to the formation of a biofilm on the metal surface in the tests with inoculum, and to a smaller trend of general corrosion with this kind of medium. SEM micrographies revealed the presence of cellular aggregates on the surface of mild steel during the experiment and the presence of deep pittings after the biofilm removal, showing that this kind of corrosion was prevalent . With 35 days of asseys, the corrosion current density increased in the presence of BRS

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-06-12T17:09:21Z No. of bitstreams: 1 ThaisPaiva.pdf: 594078 bytes, checksum: dab90ce2d1146580c6639f13c540e873 (MD5) / Made available in DSpace on 2017-06-12T17:09:21Z (GMT). No. of bitstreams: 1 ThaisPaiva.pdf: 594078 bytes, checksum: dab90ce2d1146580c6639f13c540e873 (MD5) Previous issue date: 2016-07-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Contaminated waters not only directly affect human health but also cause serious damage to the aquatic biota, causing deterioration in fish quality. The objective was to evaluate the hygienic-sanitary conditions of the water and the fresh fish from the Mearim river in BacabalMa during the rainy season, through the identification of the potentially pathogenic bacteria. A total of 54 samples of water and 54 samples of fresh fish that were colected between October 2015 and March 2016, which were submitted to the quantification of total and thermo tolerant coliformes by the thechnique of Most Probable Number (MPN/g) and Clostridium sulphite reducing research. After that, the biochemical identification of isolated bacteria coming from the Enterobacteriaceae family was performed using commercial biochemical tests. The results showed that the microbiological quality of the water and the fish is unsatisfactory due to the high contamination rates of thermotolerant coliforms, being below the microbiological quality standards, as well as the the presence of total coliforms and Clostridium sulphite reducers in considerable concentrations both in water and in fish. The water’s contamination by coliforms was significantly higher than in the fishes, in the dry season as well as in the rainy season. Escherichia coli was the bacterium with the highest frequency of isolation in water samples, both in the dry season and in the rainy season. Citrobacter diversus and Serratia odorífera also had important isolation frequency in the water samples of the two seasons. In the fish samples, the highest frequency of identification was also from Escherichia coli. Serratia odorífera and Citrobacter diversus also had relevant frequencies in the dry season. In the rainy season Escherichia coli kept the highest frequency of isolation, followed by Serratia odorífera and Citrobacter freundii. / Águas contaminadas não só afetam diretamente a saúde humana como também causam sérios danos à biota aquática, provocado deterioração na qualidade dos peixes. Objetivou-se avaliar as condições higiênico-sanitárias da água e dos peixes frescos oriundos do rio Mearim, Bacabal/MA, no período seco e chuvoso, através da identificação de bactérias potencialmente patogênicas. Foram analisadas 54 amostras de água e 54 amostras de peixes frescos coletadas no período de outubro de 2015 a março de 2016, as quais foram submetidas à quantificação de coliformes totais e termotolerantes pela técnica do Número Mais Provável (NMP/g) e pesquisa de Clostridium sulfito redutor. Em seguida a identificação bioquímica das bactérias isoladas da família Enterobacteriaceae foi realizada utilizando testes bioquímicos comerciais. Os resultados mostraram que a qualidade microbiológica da água e dos peixes estava insatisfatória, devido aos elevados índices de contaminação por coliformes termotolerantes, estando fora dos padrões de qualidade microbiológica exigidos pelas legislações vigentes, e pela presença de coliformes totais e Clostridium sulfito redutores. A contaminação da água por coliformes foi significativamente maior que nos peixes, tanto no período seco quanto no chuvoso. Escherichia coli foi a bactéria com maior frequência de isolamento nas amostras de água, tanto no período seco quanto no chuvoso. Citrobacter diversus e Serratia odorífera também tiveram importante frequência de isolamento nas amostras de água dos dois períodos. Nas amostras de peixes a maior frequência de identificação também foi de Escherichia coli. Serratia odorífera e Citrobacter diversus também tiveram frequências relevantes no período seco. No período chuvoso Escherichia coli manteve-se com maior frequência de isolamento, seguida de Serratia odorífera e Citrobacter freundii.

Routine clinical distortion product otoacoustic emission (DPOAE) tests use monaural sequential presentation of primary tones. To reduce testing time, multiple DPOAEs (mDPOAEs) can be measured by stimulating the ear with two tone pairs simultaneously. Moreover, both ears can be tested at the same time with a portable device, Sentiero (PATH medical GmbH), equipped with two sound probes. The purpose of the study was to evaluate whether mDPOAE measurements can be done in both ears simultaneously without mutual influence of primary tone pairs in the ipsilateral and the contralateral ear. Data were collected in 20 normal-hearing young adults. The DP-grams were obtained for seven f2- frequencies varying in the 1.5-8-kHz range with the level L2 set at 65 and 45 dB SPL, whereas the level L1 was adjusted according to the scissor paradigm. For each subject, a set of DP-gram data was collected using single- and multi-frequency presentations of the primaries for both monaural and binaural conditions. The mean DPOAE and noise levels collected with mDPOAE and binaural presentation conditions were highly reproducible when compared to those obtained with the single-frequency monaural paradigm. Thus, multi-frequency and binaural measurements could be applied to reduce DPOAE testing time considerably.

Ces travaux de thèse avaient pour objectifs (i) d’étudier le comportement du fer et du nickel au cours de la biominéralisation de sulfures de fer par des bactéries sulfato-réductrices et (ii) de tenter une première estimation de l’influence de l’exploitation minière sur les communautés microbiennes des sédiments de mangrove de Nouvelle-Calédonie. Pour atteindre ces objectifs, des expériences d’incubation ont été conduites en anoxie avec une espèce unique de bactérie (thio)sulfato-réductrice (i.e. Desulfovibrio capillatus) et avec un consortium de bactéries sulfato-réductrices natives de sédiments de mangrove de Nouvelle-Calédonie. Ces expériences ont été réalisées avec différentes sources de Fe(III) (i.e. goethite, ferrihydrite et citrate-ferrique) et en présence de nickel structural ou en solution. Les résultats montrent que l’activité bactérienne sulfato-réductrice (qu’elle soit synergique ou issue d’une espèce unique) conduit, dans toutes les expériences, à la formation principale de mackinawite (FeS). Ce sulfure de fer précipite sous forme de cristallites nanométriques et dont la cristallinité augmente avec la durée d’incubation. Lorsque le nickel est présent en solution, la quasi-totalité de cet élément peut se substituer au fer (i.e. substitution 4% molaire) dans la structure de la mackinawite. Ainsi, la formation d’une faible proportion de mackinawite permet de fixer la quasi-totalité du nickel initialement en solution (e.g. ratio FeS:Ni de 1). Ce mécanisme semble stable sur le long terme (pas de relargage de nickel en solution) et il accélère la croissance cristalline de la mackinawite, ce qui engendre une stabilité accrue de ce minéral. Ces résultats soulignent le rôle efficace des bactéries sulfato-réductrices dans la formation des sulfures de fer de type mackinawite et dans le piégeage du nickel, suggérant une stabilisation de cet élément dans les sédiments de mangrove et la limitation de sa biodisponibilité. Ceci pourrait expliquer les résultats de l’étude comparative des consortiums bactériens autochtones qui ne permet pas de déceler d’impact de l’activité minière sur les communautés bactériennes sulfato-réductrices présentes en Nouvelle-Calédonie. / The aims of the present work were (i) to study the behavior of iron and nickel in the biomineralization of iron sulfides by (thio)sulfate-reducing bacteria and (ii) to estimate the influence of open-cut mining activities on microbial communities development in mangrove sediments in New Caledonia. To achieve these objectives, incubation experiments were conducted under anoxic conditions with the (thio)sulfate-reducing bacteria (i.e. Desulfovibrio capillatus) and a consortium of sulfate-reducing bacteria native mangrove sediments of New Caledonia. These experiments were carried out with different Fe(III) precursors (i.e. goethite, ferrihydrite and ferric citrate) and in the presence of structural or soluble nickel. The results show that the sulfate-reducing bacterial activity leads, in all experiments, to the formation of mackinawite (FeS). This iron sulfide precipitates as nanosized crystallites that increase in size with incubation time. When nickel is present in solution, the total soluble amount can be substituted to iron (i.e. replacing 4 mol%) in the structure of mackinawite. Thus, the formation of a small proportion of mackinawite scavenged total soluble amount of nickel initially present in solution (e.g. FeS:Ni ratio of 1). This sequestration mechanism appears to be stable over time (no nickel was released in solution) and accelerates the crystal growth of mackinawite, leading to the stabilization of this mineral. These results highlight the effective role of sulfate-reducing bacteria in the biomineralization of iron sulfides such as mackinawite and in the sequestration of nickel, suggesting a stabilization of this element in mangrove sediments and limitation of its bioavailability. These results could explain the absence of negative impact of open-cut mining activities on the sulfate-reducing bacterial communities present in New Caledonia.

Vanadium compounds have been reported to cause numerous toxicological effects including NAD(P)H oxidation and lipid peroxidation. The purpose of this thesis is to determine the active form of vanadium in causing these effects, and to determine any possible free radical involvement in these processes. Vanadium-stimulated oxidation of NADH was studied spectrophotometrically and by electron spin resonance spectroscopy. In 25 mM sodium phosphate buffer at pH 7. 4, vanadyl , (V(IV)), is slightly more effective in stimulating NADH oxidation than was vanadate (V(V)). Addition of a superoxide generating system, xanthine/xanthine oxidase, results in a marked increase in NADH oxidation by vanadyl, and to a lesser extent, by vanadate. In contrast, addition of hydrogen peroxide did not change the NADH oxidation by vanadate, but greatly enhanced NADH oxidation by vanadyl. Use of the spin trap DMPO in reaction mixtures containing vanadyl and hydrogen peroxide or a superoxide generating system resulted in the detection by ESR of hydroxyl radical. Hydroxyl radical was also detected in the system containing vanadate plus superoxide. It was found that superoxide is capable of reducing vanadate to vanadyl, and that vanadyl is capable of reaction with hydrogen peroxide in a Fenton-like mechanism to produce hydroxyl radical. Hydroxyl radical is suggested to be the active species involved in NADH oxidation. Other reductants, such as thiols, are also capable of supporting vanadate-stimulated NADH oxidation . The above results indicat that ability of vanadium to act in a Fenton-like mechanism is an important process in the vanadium-stimulated oxidation of NADH. Vanadyl was found to be the active form of vanadium involved in initiating and stimulating lipid peroxidation in purified and partially purified fatty acid micelle preparations. Hydroxyl radicals were shown to be involved in initiating diene conjugation when vanadyl and hydrogen peroxide were added together in the reaction mixture. Furthermore, hydroxyl radicals were shown to be generated in the vanadyl-catalyzed decomposition of fatty acid lipoperoxides. The results of this study indicat that the ability of vanadium compounds to oxidize NADH and to stimulate lipid peroxidation are related by the common mechanism of hydroxyl radical production from the reaction of vanadyl with hydrogen peroxide.

Students’ experience of stress is generally considered to be an isolated problem, caused by school work. Students’ experience of stress at school can also be affected by exterior influences. This research aims to discover what factors Swedish students, age 13 – 16, experience as stressful. It also aims to describe how students believe this stress can be reduced. This project originated from a request from a secondary school. A questionnaire was used to map the different stress factors. Interviews enabled greater understanding of these factors and what students themselves believe can reduce the stress. The gathered material was interpreted in several steps by the use of ad hoc methods. The result shows that half of the students experience stress every week. The main causes are lack of time and demands. They lack “free time”, which enables the body to recover from the stress. The students desire management, including guidance from parents concerning prioritising and setting limits. The school should help the students to develop study techniques. The stress is caused by a feeling of not being able to live up to and deal with own and exterior demands. It can be reduced by planning (enabling “free time”), influence (co-operation), personal development (improvement of self-esteem and identity) and management (guidance, limitations, acceptance and development). / Elevers upplevda stress i skolan ses ofta som ett isolerat problem som framkallas och påverkas under skoltid. Upplevelser av stress i skolan kan även bero på andra faktorer som elever påverkas av utanför skoltid. Studien syftar till att kartlägga olika faktorer som elever i årskurs 7-9 upplever som stressande och hur de tror att stressen kan reduceras. Detta arbete har utgått från en frågeställning som framförts av en skola. En enkät användes för att kartlägga olika stressfaktorer. Intervjuer gav djupare förståelse för de olika stressfaktorerna och hur eleverna tror att den upplevda stressen kan reduceras. Det insamlade materialet tolkades i flera steg med ad hoc-metoder. Resultatet visar att hälften av eleverna känner sig stressade varje vecka. Elevernas största stressfaktorer är tidsbrist och krav. De saknar ”fri tid”, som ger kroppen återhämtning från stress. Eleverna efterlyser ledarskap, hjälp från föräldrar att prioritera och sätta gränser samt att skolan ska utveckla elevernas studietekniker. Stressen orsakas av en känsla att inte kunna leva upp till och hantera egna och omvärldens krav. Reducering av stressen kan ske genom planering (skapande av ”fri tid”), inflytande (samplanering), personlig utveckling (stärkt självkänsla och identitet) och ledarskap (ledning, gränssättning, acceptans och utveckling).