Iron corrosion is the most important economic and aesthetic problem facing utilities. In the water distribution system, problems caused by iron corrosion include "red water", scale buildup, and pipe failures. It is necessary to improve our mechanistic understanding of anaerobic iron corrosion in order to better address these concerns. Experiments were conducted to investigate the effect of soluble constituents (Fe2+, PO43-, and NH4+) on H2 evolution during anaerobic iron corrosion. At pH 7.0 when sulfide was absent, variable Fe2+ did not have much influence on H2 release rates, whereas PO43- and NH4+ promoted H2 evolution. If present, soluble sulfide controlled H2 release rates in the solutions with Fe2+ or PO43-; however, NH4+ and S2- combined to inhibit H2 release. A simplistic empirical model was developed that fit data on corrosion rates from previous researchers studying effects of sulfate-reducing bacteria (SRB) on iron corrosion. As a whole, the experimental data and the model results support the notion that water quality controls iron corrosion rates in the presence of SRB. The practical relevance of previous research is somewhat in doubt given the atypical levels of nutrients used in relation to those actually present in water and wastewater. A second phase of research was aimed at exploring the equilibrium and kinetic aspects of iron corrosion in the presence of phosphate. The hypothesis that anaerobic iron corrosion is influenced by low pressure H2 (<1 atm) buildup was examined. At pH 2.75 and pH 7.0 in the presence of 100 mg/L P-PO43-, variations in H2 release were measured under different circumstances. Addition of PO43- formed a protective film, possibly vivianite Fe3(PO4)2, on the iron surface that eventually stopped H2 release. However, results were consistent with the idea that corrosion is an irreversible process that is relatively insensitive to low level H2 (<1 atm). Possible alternative explanations were provided to reconcile the past research data that purportedly demonstrated that removal of H2 increased corrosion rates. A reaction that caused "decay" of H2 in the presence of high phosphate was discovered that can not be readily explained. / Master of Science

Master of Science / Department of Civil Engineering / Natalie Mladenov / The detrimental health effects of arsenic (As) contamination have motivated the study of As mobility around the globe. The variability in naturally occurring As concentration is due to variation in geology and climate. In arid environments with high evaporation, ecohydrology and As desorption under alkaline pH are thought to be responsible for high As concentrations. In reducing groundwater, on the other hand, microbial iron (Fe) reductive dissolution is known to release As into solution. In such environments, As-sulfide minerals precipitation and vegetation uptake could contribute to re-distribution of As. The Okavango Delta is an arid-zone wetland punctuated by ten of thousands of islands, and the reducing groundwater beneath these islands have dissolved As as high as 3000 µg•L[superscript]-1. Ecohydrologic controls are thought to contribute to the elevated As level; however dissolution of Fe-containing sediments has been proposed as the initial step in releasing As from sediment to the groundwater. To test the consistency of the hypothesized mechanisms, four islands were sampled in January 2013. The goal of this thesis is to: 1) provide more evidence on the zones of elevated As in groundwater of four islands, 2) gain understanding on the influence ecohydrology (i.e., evapotranspiration) on high As in groundwater, 3) evaluate the sediment of microbial community composition, and 4) gain new insights into the behavior of DOM along the groundwater flow path. The findings show zones of elevated As in all four islands. The ecohydrologic controls provide information on the location of high As and solute accumulation. Microbial analyses suggest DNA sequences collected were grouped within lineages that contain organisms capable of dissimilatory Fe reduction and sulfate reduction. This supports evidence from previous study that sulfide produced by microbial sulfate reduction is available for As-sulfide mineral formation. The variation of DOM characteristics could influence As solubility and reactivity. In addition, carbonate alkalinity and increase pH may contribute to As mobility further along the flow path. In this arid and reducing groundwater, we find that ecohydrologic and biogeochemical processes have a fundamental role in As mobility.

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

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.

The purpose of this study is to use vertical-flow constructed wetlands (VFCW) microcosm systems to investragte the removal efficiencies of sulfate. The system was located on the campus sewage treatment plant. nn National Sun Yat-sen University. In this study, two media, gravel and peat, were installed in four different systems. The two system with same media were separated into vegetated and non-vegetated (control) ones respectively. In the test runs, the operation methods included batch type filled with water, continuous flow and integrated vertical flow constructed wetland (IVCW) with continuous flow. In batch type test, it was run under an initial concentrations of SO42--S about 500 mg/L. The experimental results showed that the removal efficiencies were increased with increasing COD concentrations. Under the same conditions but with continuous flow operation, the removal efficiencies of SO42--S were lower than the batch type one, which 80% could be reached. The best system for operation was P1 (peat with vegetated), in which the removal effciency reached 90%. The experimental results also showed that the vegetated systems presented higher removal efficiencies of sulfate than the non-vegetated ones. In addition, this research were increased the concentrations of SO42--S and COD to about 1200 mg/L and 4000 mg/L respectively. The experimental results showed that the IVCW treatment system could achived greater efficiency than VFCW treatment system. The experimental in depth research test run indicated that the anaerobic condition did not affect the removal efficiencies of ammonia by using batch type. However, nitrification was the main reaction of ammonia to nitrate in the continuous flow type systems. When ORP values were found below the -300 mV, the sulfate began to be drcreased. It was believed that if the anaerobic condition were well be established, while the organic carbon could be contented in this system, the sulfate reducing bacteria (SRB) might live, and then sulfate could be removed. The effect of temperature on sulfate removal was generally established in this study. According to the experimental results, it was found that the activity of SRB motility was higher in higher temperature (35¢J) than that in lower temperature (25¢J).

Naturally occurring bacterial populations are capable of detoxifying chlorinated compounds and immobilizing the radionuclide uranium via reductive processes. This study addressed the following three knowledge gaps in the fields of chlorinated solvent and uranium bioremediation, 1) the risks and benefits of coupling bioremediation with thermal treatment for clean-up of chlorinated ethene-contaminated sites, 2) the accuracy of available techniques for the monitoring of chlorinated solvent bioremediation, and 3) the role of gram positive Desulfitobacterium spp. in uranium immobilization. Experiments demonstrated that thermal treatment increases electron donor availability, but the increased electron donor was not used to fuel reductive dechlorination and was actually consumed for methanogenesis. Two approaches for monitoring chlorinated solvent bioremediation were investigated, molecular techniques and compound-specific isotope analysis (CSIA). Results demonstrated that while Dehalococcoides (Dhc) gene expression was up-regulated under conditions inhibitory to dechlorination, the isotope effects associated with dechlorination reactions catalayzed by Dhc populations in consortia and in pure cultures were similar. U(VI) reduction by multiple Desulfitobacterium isolates was demonstrated. Interestingly, while almost all U(VI)-reducing populations have been reported to produce uraninite (UO2), the product of U(VI) reduction by Desulfitobacterium isolates was a unique form of insoluble mononuclear U(IV).

Thesis (MSc., Geology) -- Queen's University, 2008. / Includes bibliographical references.

No

Coal-generated acid mine drainage (AMD) is characterized by low-pH waters with excessive loads of dissolved species such as SO4, Fe, Al and Mn along with other elements of environmental concern (i.e. Cd, As, Cr, Ni, Pb, Se and Cu). To mitigate this problem, anaerobic sulfate reducing bioreactors (ASRB) have been implemented as a technology for passive treatment systems that utilize low-cost organic substrates to stimulate biologically enhanced contaminant sequestration. Previous work has identified the establishment of diverse microbial communities in which a hierarchal chain of substrate degradation processes is essential in developing sustainable environments to produce long-lived sulfate-reducing microbial (SRM) populations. In this study, to determine the optimal mixture of substrate types, alternating ratios of herbaceous (ie. leaves, grass, spent brewing grains) and ligneous (i.e. maple wood chips and saw dust) reactor matrices were tested. Five bioreactors along with one control reactor containing only limestone were constructed at the Tab-Simco abandoned mine land (AML) site in southern Illinois, USA. The field experiments were monitored over ~ one year (377 days) to evaluate the physical, geochemical and microbiological parameters which dictate ASRB efficiency in remediation of AMD contaminants. Results from this experiment documented contaminant removal in all reactors. However, the bioreactors established SRM populations that contributed to enhanced removal of SO4, Fe, and trace metals (i.e. Cu, Cd, Zn, Ni). Geochemical assessment of the aqueous environments established within the bioreactors suggested multiple pathways of contaminant sequestration. This included the formation of Fe-oxyhydroxide precipitates, adsorption, co-precipitation (e.g. Zn/Ni-Ferrites) and bio-induced sulfide mineralization. Activity of the SRMs was dependent on temperature, with bioreactors exhibiting decreases in both effluent sulfide concentrations and 34S-depletion of sulfate during low-T months (i.e. T < 10°C). Overall, maximum remediation of dissolved constituents SO4, Fe, Al and Mn was obtained in the predominantly herbaceous bioreactors. Extrapolation of our results to the full-scale Tab-Simco bioreactor indicated that, over the course of one year, the herbaceous bioreactors would remove ~75,600 kg SO4, 21,800 kg Fe, 8000 kg Al, and 77 kg Mn. This represents a 21.7 wt%, 41.5 wt%, 9.4 wt% and 81.8 wt% increase in SO4, Fe, Al and Mn removal over dominantly ligneous bioreactors, respectively. Although the overall Fe removal within the limestone control reactor reached 44.5 mol%; removal of 19.5 mol% SO4 and 36.9 mol% Al from influent AMD were significantly less when compared to the bioreactors. These results imply that ASRB technologies are promising in remediation of coal-generated AMD and increasing herbaceous content of bioreactors can significantly enhance contaminant sequestration. However, geochemical results also displayed seasonal variation in redox gradients within our field ASRB's which may induce dissolution of the redox sensitive phases produced within bioreactors. Furthermore, optimal microbial-mediated sulfate reduction may be inhibited by the high surface areas of the abundant Fe/Al-oxyhydroxides which dominate the system. Therefore, to enhance ASRB remediation capacity, future designs must optimize not only the organic carbon substrate but also include a pretreatment phase in which the bulk of dissolved Fe/Al-species are removed from the influent AMD prior to entering the bioreactor.

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