Made available in DSpace on 2015-04-11T13:47:49Z (GMT). No. of bitstreams: 1 denis de freitas.pdf: 1275633 bytes, checksum: 32965674ec224ae9adc1687ed644f52b (MD5) Previous issue date: 2013-12-16 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The study of soil as a corrosive medium is considered of great importance, due to the large number of pipes and tanks fitted inside. The deterioration of these structures over the years, can pose a real problem for the economy and for the environment. Several methods have been proposed to study and monitor corrosion processes, such as mass loss tests, solution analysis, electrochemical and microbiological analyzes. In this research we used the AISI 1020 steel due to its chemical composition is similar to that of most steel pipelines - Case Urucu- Coari - Manaus. In this context, it was determined the corrosivity of a characteristic soil in the Amazon region for analytical and biological techniques. The geotechnical characterization of Amazonian soil held by determining the density, liquidity limits and plasticity , and grain size , according to the rules of the Brazilian Association of Technical Standards (ABNT). For the analysis of mass loss worked with fresh samples and autoclaving. For fresh samples were made three kinds of tests: one placed in a jar containing steel 1020 and buried in soil in nature , and the other two samples with steel buried in soil aqueous extract (with and without cleaning steel isopropanol ). Another analysis with two sterile samples. For the calculation of the rate of corrosion (NACE standards -RP -07 -75 and ASTMG1 -90) were performed daily measurements over a period of 30 days. We analyzed the presence of micro-and macronutrients by atomic absorption spectrophotometry in the soil, the concentration of the chemical elements in the soil aqueous extract fluorescence x-rays by total reflection and microbiological analysis to identify the genus and species of corrosive bacteria. The geotechnical results were : a) the density equal to 2.571 g / cm ³ b ) grading curve indicating clay matrix of the order of 76.08 % , and c ) liquid limit of 83 % and equal to 41 % LP, so an IP = 42%. This set of values framed the natural material, according to the classification of the Transportation Research Board (TRB) in group A- 7 on the clay soils. Referring to the analysis of weight loss, it is indicated that severe resolution of the samples according to comparative standard NACE -RP -07 -75, both for fresh samples and for sterilized samples , with one must underline that the samples sterilized obviously had lower rates than in nature . Analyses of soil micro and macronutrients identified elements which give average values for cation exchange capacity presenting colloidal particles that give the clay soil more aggressivel. Since the technique of fluorescence x- rays identified in this study key elements such as S and Cl, elements corrosive agents. Microbiological analysis identified the genus of bacteria Thiobacillus Thiooxidans, which oxidize S (sulfur) or S compounds to sulfate, with simultaneous production of sulfuric acid, which acts as a corrosive agent. In this perspective it appears the good performance of the study of corrosion of AISI 1020 steel in natural clayey soil in the Amazon region. / O estudo do solo como meio corrosivo é considerado de grande importância, em função do elevado número de tubulações e reservatórios instalados dentro do mesmo. A deterioração dessas estruturas, com o passar dos anos, pode representar um problema real para a economia e para o meio ambiente. Diversos métodos têm sido propostos para estudar e monitorar processos de corrosão, tais como: ensaios de perda de massa, análise de solução, análises eletroquímicas e microbiológicas. Nesta pesquisa utilizou-se o aço AISI 1020, devido a sua composição química ser similar aos aços da maioria dos oleodutos e gasodutos caso do gasoduto Urucu-Coari-Manaus. Neste contexto, determinou-se a corrosividade de um solo característico da região amazônica por técnicas analíticas e biológicas. A caracterização geotécnica do solo amazônico realizou-se por meio da determinação da massa específica, limites de liquidez e plasticidade, e granulometria, de acordo com as normas da Associação Brasileira de Normas Técnicas (ABNT). Para as análises de perda de massas trabalhou-se com amostras in natura e com esterilização em autoclave. Para as amostras in natura fizeram-se três tipos de análises: uma colocada em um frasco contendo o aço 1020 e enterrada no solo in natura; e as outras duas amostras com o aço enterrado em extrato aquoso do solo (sem e com limpeza do aço com isopropanol). Outra análise com duas amostras esterilizadas. Para os cálculos da taxa de corrosão (normas NACE-RP-07-75 e ASTMG1- 90) realizaram-se medidas diárias em um período de 30 dias. Analisou-se a presença de micro e macronutrientes por espectrofotometria de absorção atômica no solo, a concentração dos elementos químicos no extrato aquoso do solo por fluorescência de raios-x por reflexão total e análise microbiológica para identificação do gênero e espécie de bactérias corrosivas. Os resultados geotécnicos foram: a) a massa específica igual a 2,571 g/cm³; b) curva granulométrica indicando matriz argilosa da ordem de 76,08%; e c) limite de liquidez de 83% e LP igual a 41%, portanto um IP = 42%. O conjunto desses valores enquadrou o material natural, conforme a classificação do Transportation Research Board (TRB), no grupo A-7, relativo aos solos argilosos. Referente à análise de perda de massa, esta indicou que se trata de amostras severas segundo a resolução da norma comparativa da NACE-RP-07-75, tanto para as amostras in natura como para as amostras esterilizadas, havendo um ressalvo de que as amostras esterilizadas apresentaram obviamente taxas mais baixa do que as in natura. As análises de micro e macronutrientes do solo identificaram elementos que conferem valores médios em capacidade de troca catiônica apresentando partículas coloidais que conferem ao solo argiloso maior agressividade. Já a técnica de fluorescência de raios-x identificaram elementos fundamentais para este estudo como S e Cl, elementos agentes de corrosividade. A análise microbiológica identificou o gênero de bactérias Thiobacillus Thiooxidans, capazes de oxidar S (enxofre) ou compostos de S a sulfato, com simultânea produção de ácido sulfúrico, que age como agente corrosivo. Nesta perspectiva verifica-se o bom desempenho do estudo da corrosão do aço AISI 1020 no solo natural argiloso da região amazônica.

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Orientador: Laura Maria Mariscal Ottoboni / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Biologia / Made available in DSpace on 2018-07-23T19:15:17Z (GMT). No. of bitstreams: 1 Novo_MariaTeresaMarques_D.pdf: 4388960 bytes, checksum: 4e9cc7ee25e2a967d6cd5387992b880d (MD5) Previous issue date: 1998 / Doutorado / Genetica de Microorganismos / Doutor em Ciências Biológicas

Chemical inhibition of acid production by acidophilic thiobacilli was tested using a variety of metals and chelators (alone and in combination) including Hg(II), Ag(I), Co(II), Mo(VI), Cu(II), Zn(II), Cd(II), EDTA and NTA. When tested individually, Hg(II) and Ag(I) showed toxic effects at concentrations of 10-5 M and below; Cd(II), Zn(II) and NTA were noninhibitory at millimolar concentrations. Combination experiments showed both synergistic and antagonistic effects on chemical toxicities. Antagonism was apparent in experiments involving Cu(II)-EDTA, Cu(II)-Fe(III) and Cu(II)-Co(II). Synergism was apparent in experiments involving simultaneous addition of Mo(VI), Cu(II), Co(II) and Zn(II). In general, inhibitors either completely blocked or delayed the onset of acid production. In those cases where delayed reactions were observed, acid production began following an acclimation period on the order of days to weeks. Acclimation and metals speciation experiments suggest that adaptation events are due to biologically dependent changes in inhibitor speciation.

Acidithiobacillus ferrooxidans is a gram-negative bacterium that is able to extract energy from oxidation of Fe²⁺ and reduced sulfur compounds and fix carbon dioxide from atmosphere. The facts that A. ferrooxidans thrives in acidic pH (~2), fixes carbon dioxide from the atmosphere and oxidizes Fe²⁺ for energy make it a good candidate in many industrial applications such as electrofuels and biomining. Electrofuels is a new type of bioprocess, which aims to store electrical energy, such as solar power, in the form of chemical bonds in the liquid fuels. Unlike traditional biofuels made from agricultural feedstocks, electrofuels bypass the inefficient photosynthesis process and thus have potentially higher photon-to-fuel efficiency than traditional biofuels. This thesis covers the development of a novel bioprocess involving A. ferrooxidans to make electrofuels, i.e. isobutyric acid and heptadecane. There are four major steps: characterization of wild-type cells, engineering of medium for improved electrochemical performance, genetic modification of A. ferrooxidans and optimization of operating conditions to enhance biofuel production. Each is addressed in one of the chapters in this thesis. In addition, applications of A. ferrooxidans in biomining processes will be briefly discussed. An economic analysis of various applications including electrofuels and biomining is also presented. Wild-type A. ferrooxidans were first characterized in both batch and continuous cultures. A modified 9-K medium suggested by American Type Culture Collection (ATCC) was used as a starting point which has 72 mM Fe²⁺ at pH 1.8. The Fe²⁺ concentration and pH were varied in the experiments to assess their impacts on growth rate, cell yield (g cells/g Fe²⁺) and maintenance (energy used to keep cell viability). Citrate was added to the growth medium to dissolve precipitates which can be problematic in a continuous operation. It was found out that cells exhibited higher cell yield (g cells/g Fe²⁺) and lower maintenance with higher pH and addition of citrate. This indicates that cells grow in a more energy-efficient manner at such conditions since cells spend less energy in maintenance and more energy in biomass formation. Next the growth medium containing 72 mM Fe³⁺ and 70 mM citrate at pH 2.2 was explored during the electrochemical reduction of Fe³⁺. It turned out that electrochemical reduction of Fe³+ could not be carried out effectively due to a low electrolyte conductivity and low energy density of the medium. Citrate was also found to negative affect electrochemical performance due to a strong complexation with Fe³⁺. The conductivity was improved by adding 500 mM Mg²⁺ to the medium. Vanadium was used as an alternative redox mediator that has a much better solubility than Fe³⁺ to improve the energy density. Genetic modification was achieved by introducing genes from two foreign pathways i.e. valine synthesis and fatty acid synthesis into A. ferrooxidans to enable cells to produce either isobutyric acid (IBA) or heptadecane. Transformed cells were characterized based on the findings in wild-type cells. Isobutyric acid production was found to increase with increasing pH and Fe²⁺ concentration and addition of citrate. Further optimization of the growth medium was done by increasing Fe²⁺ to 288 mM, holding pH at 2.2 and using gluconate as the iron chelator instead of citrate. An economic analysis was performed on the electrofuel process and applications of genetically modified A. ferrooxidans in copper biomining processes. At electricity prices of $0.05/kWh, further improvement in biological efficiency needs to be achieved before the electrofuel process may become economically viable. The use of genetically modified cells in copper biomining process could open new opportunities to co-produce valuable chemicals and copper from the reduced material associated with the copper ores. The chemicals co-produced during copper processing could be sold for additional revenue or used on-site.

Thesis (Ph.D.)--University of Tulsa, 1990. / Bibliography: leaves 86-91.

Thesis (Ph.D.)--University of Tulsa, 1990. / Bibliography: leaves 125-132.

Inorganic sulfur-oxidising Bacteria are present throughout the Proteobacteria and inhabit all environments of Earth. Despite these facts they are still poorly understood in terms of taxonomy, physiology, biochemistry and genetics. Using phylogenetic and chemotaxonomic analysis two species that were erroneously classified as Thiobacillus trautweinii spp. in 1921 and 1934 are in fact novel chemolithoheterotrophic species for which the names Pseudomonas trautweiniana sp. nov. and Achromobacter starkeyanus sp. nov. are proposed, respectively. These species were found to oxidise thiosulfate in a “fortuitous” manor when grown in continuous culture and increases in maximum theoretical growth yield (YMAX) and maximum specific growth rate (μMAX) were observed. Cytochrome c linked thiosulfate-dependent ATP production was confirmed in both species, confirming “true” chemolithoheterotrophy. Evidence is presented that the ATP concentration governs the benefits of chemolithoheterotrophy. There were significant changes in enzyme activities, including enzymes of the TCA cycle that might be affecting amino acid synthesis. This is strong evidence that chemolithoheterotrophy gives a strong physiological boost and evolutionary advantage over strictly heterotrophic species. An autotrophic species that was historically placed in Thiobacillus was also shown to be a novel species for which the name Thermithiobacillus parkerianus sp. nov. is proposed. The enzyme profiles of Thermithiobacillus parkerianus differed significantly between different inorganic sulfur growth substrates and was the first time all TCA cycle enzymes were assayed in a member of the Acidithiobacillia. The properties of thiosulfate dehydrogenase varied significantly between Pseudomonas sp. Strain T, Achromobacter sp. Strain B and Thermithiobacillus sp. ParkerM both in terms of optimal parameters and the effect of inhibitors. This evidence adds to the increasing body of work indicating there to be at least two thiosulfate dehydrogenases present in the Bacteria.

Ingeniera Civil Química. Ingeniera Civil en Biotecnología / Este trabajo se realizó en el Laboratorio de Biohidrometalurgia del Departamento de Ingeniería Química y Biotecnología de la Facultad de Ciencias Físicas y Matemáticas de la Universidad de Chile. El objetivo principal de este estudio experimental fue determinar el efecto del metabolismo de bacterias azufre-oxidantes en la corrosión del hormigón influenciada por microorganismos (MIC). La motivación se enmarca en la disminución del impacto ambiental de los proyectos de infraestructura, al aumentar la durabilidad de las estructuras de hormigón, previniendo la componente bacteriana de la corrosión. El hormigón es el sistema constructivo más utilizado y extendido en la actualidad, por lo que el impacto de la corrosión de este es importante en los análisis de costos de distintos proyectos, principalmente en cañerías de hormigón, represas hidroeléctricas y plantas de tratamiento de aguas servidas. En la literatura se encuentran estudios que muestran la presencia de Acidithiobacillus thiooxidans en hormigón corroído sin embargo no existen estudios experimentales que busquen estimar la influencia de la actividad bacteriana en el proceso de corrosión. En la primera etapa, se aislaron e identificaron bacterias desde hormigón corroído, utilizando técnicas de cultivo bacteriano y CARD-FISH, encontrándose presencia de las bacterias azufre oxidantes A. ferrooxidans y A. thiooxidans En la segunda etapa, se realizaron cultivos A. thiooxidans con azufre y cemento endurecido como sustratos, midiendo la concentración en el medio de cultivo de sulfatos por turbidimetría y de ion calcio por absorción atómica, pudiendo concluir que existe una componente bacteriana de la corrosión que acelera el proceso puramente electroquímico, cuya cuantificación no fue parte de este estudio.

Resumo: A disposição em solos agrícolas e florestais de lodos resultantes de estações de tratamento de esgoto vem sendo amplamente revisada e questionada nos países que se utilizam desta prática. Embora isto venha a resolver um problema sério de falta de espaço e alto custo de destinação do lodo, e ainda substituindo parcialmente as necessidades de adubação química, os problemas de acréscimo de metais pesados aos solos através do lodo e a presença de patógenos se constituem hoje nos principais fatores de restrição de uso. Apesar deste método de disposição não ser muito utilizado ainda, a tendência é de aumento, pois houve um crescimento expressivo no número de Estações de Tratamento de Esgoto, criando uma demanda para destinação do lodo gerado. Com relação aos níveis de metais pesados, a preocupação tem sido quanto aos efeitos cumulativos destes metais, pois a legislação dos países onde a disposição agrícola do lodo já é utilizada tende a ficar cada vez mais rígida, baixando os limites aceitáveis pela legislação. Este trabalho avaliou a eficiência de bio-lixiviação de metais pesados por bactérias do gênero Thiobacillus em lodos ativados, assim como caracterizou química e biologicamente o lodo antes e depois do processo de bio-lixiviação, e trabalhou nos isolamentos de microrganismos nativos do lodo capazes de lixiviar metais pesados. As eficiências de bio-lixiviação alcançadas para os quatro elementos considerados neste estudo foram: Cd (95%); Pb (95%); Cu (95%), Zn (50%). As propriedades fertilizantes não foram afetadas pelo processo. Palavras-chave: Thiobacillus, metais-pesados, biohidrometalurgia, biolixiviação, lodos aeróbios, disposição agrícola