Thesis (Ph. D.)--Ohio State University, 2005. / Title from first page of PDF file. Document formatted into pages; contains xvii, 233 p.; also includes graphics (some col.). Includes bibliographical references (p. 185-192). Available online via OhioLINK's ETD Center

The Redwater Production Area (RPA) is an established oil field located north of Edmonton in central Alberta. Recent assessments indicate that substantial amounts of hydrocarbon contaminated soil exist in the RPA as a result of the use of flare pits, ecological ponds, product spills and pipeline leaks. Alternative remedial technologies may reduce the quantity, cost, and ultimately the long-term liabilities associated with the current practice of landfill disposal. The purpose of this thesis is to assess the viability of accelerated biopile soil treatment as a remedial methodology in the rehabilitation of contaminated soil in the RPA. The thesis includes a literature search, a bench scale treatability and pilot biopile experiment and concludes with a summary of the viability of biopiling to be employed as part of a multi-year/multi-site remedial initiative. Construction of the Redwater Soil Treatment Facility began in 2008 with treatment and recycling operations commencing in early 2009.

Thesis--University of Wisconsin--Stevens Point, 2004. / Includes bibliographical references (leaves 108-110).

Biopiles are a common treatment for the ex-situ remediation of contaminated soil. Much research has been carried out on understanding and modelling of bioremediation techniques related to biopiles, but hitherto no study has attempted to model the effect on a biopile by its ambient surroundings. A hydraulics-based approach to simulating a biopile in the context of its ambient surroundings is presented in this study, taking into account physical, chemical and biological processes within the pile, external conditions of wind and temperature, the location of aeration pipes and venting pressure, and considering the spatial distribution of treatment as well as contaminant within the pile. The simulation approach was based upon a fluid flow model which couples Eulerian multiphase flow model and Darcy’s Law for immiscible fluid flow through porous media, a species transport model integrating advection, diffusion/dispersion and biodegradation, and a heat transfer model considering the interphase temperature equilibrium. A Computational Fluid Dynamics (CFD) system has been developed to solve this set of mathematical models by applying the commercial CFD package FLUENT, and various trial simulations have been carried out to examine the potential of the hydraulics approach for practical applications. The simulation produces reasonable results: the biodegradation process relates to the temperature within the pile, and the temperature in turn relates to wind speed and aeration details; due to the various fluid flow patterns, the contribution of each remediation mechanism (contaminant loss to atmosphere via pile surface, contaminant loss to aeration pipe and biodegradation) varies according to the aeration method; contaminant interphase transfer between different pairs of phases have greatly different impacts on contaminant removal. A number of counter-intuitive results are presented, indicating that simulations of this type will give valuable insight into the practical design of biopiling systems. The simulation system also allows the total environmental footprint of biopiling to be considered, examining not just degradation of contaminant but also its removal via volatilization and the energy used in heating air for venting. Further, the application of the approach formulated in this study is not limited to biopiles, but can also be expanded to related in situ bioremediation techniques.

Une biopile convertit l'énergie disponible dans un substrat biodégradable directement en électricité tout en diminuant sa demande chimique en oxygène (DCO). Ce projet de doctorat a évalué, à une échelle laboratoire, comment cette technologie pouvait être adaptée au traitement du lisier de porc. La construction d'une première génération de biopiles à compartiment unique a été réalisée. Différents supports de croissance bactérienne ont été essayés à l’intérieur du compartiment anodique pour augmenter la superficie sur laquelle les bactéries peuvent se développer et ainsi favoriser la production d’électricité. Parmi les différents supports bactériens utilisés au cours de ce projet, des granules de charbon activé se sont révélés être le meilleur choix. L’analyse des communautés microbiennes extraites des supports de croissance a révélé que seulement quelques genres bactériens provenant du lisier, notamment le genre Desulfuromonas, sont responsables des activités électriques d’une biopile alimentée avec cet effluent d’élevage. Les mécanismes de transfert des électrons entre les bactéries et l’anode s’expliquent essentiellement par la formation d’un cycle de soufre interne dans les biopiles. Après avoir constaté l’empoisonnement de la cathode dans les biopiles à compartiment unique, les travaux se sont poursuivis en réalisant des biopiles à compartiment double. Par souci de rentabilité pour les futures biopiles commerciales, des cathodes maisons à base d’acier inoxydable plaqué par galvanoplastie avec du platine ont été développées. De même, pour augmenter le potentiel des biopiles, du peroxyde d’hydrogène a été retenu comme milieu oxydant dans le compartiment cathodique. Ces biopiles ont fourni en service continu une sortie de puissance volumique moyenne de 63 W•m-3, ce qui figure parmi les meilleurs résultats présentés à date dans la littérature avec une eau usée comme carburant. Les essais réalisés avec ces biopiles ont permis d'observer un abattement de la DCO de 60 %. De plus, les odeurs dégagées par un lisier traité dans une biopile sont, en moyenne, huit fois moins intenses que celles émises par un lisier brut et on note qu’un lisier traité contient dix fois moins de bactéries pathogènes qu’un lisier brut. / Microbial fuel cell (MFC) is a new green technology that converts energy available in a bio-convertible substrate directly into electricity while decreasing its chemical oxygen demand (COD). As MFC seemed to be very promising, this Ph.D. project was devoted to investigate, at laboratory scale, how this technology could perform if swine liquid manure was used as fuel. A first generation, single chamber MFC (SCMFC), has been designed. Various support media were brought into SCMFCs anodic chamber to increase surface area on which bacteria may grow. Through this project, best electrical results were achieved using activated coal pellets as bacterium support medium. Bacterial communities extracted from selected support media were analyzed. These analyzes revealed that only few bacterium genera coming from raw liquid manure are responsible for electrical activities and Desulfuromonas genera was particularly involved in the process. With these bacteria, an internal sulphur cycle is involved to explain electron transfer mechanisms. While platinum based electrode was used as cathode in SCMFC, electrode poisoning yielded only weak power outputs. To overcome this problem, dual-chamber MFCs (DCMFC) were designed. Economical concerns for future commercial DCMFCs led to development of cathodes built around stainless steel wire meshes electro-plated with platinum. In addition, to increase DCMFC potential, hydrogen peroxide solution was retained as oxidizing medium in cathodic chamber. In continuous operation, 63 W•m-3 power output was provided with these 350 mL capacity DCMFCs, which appears to be among best results presented so far in literature with waste water as fuel. Tests carried out with these DCMFCs showed COD reduction of 60 %. Moreover, treated liquid manure odour emissions are, on average, 8 times weaker than those released by raw liquid manure. Finally, it was noted that treated liquid manure contained 10 times less pathogenic bacteria than raw liquid manure.

Les biopiles enzymatiques miniatures représentent un potentiel important pour la future génération de dispositifs médicaux implantables, utilisés pour le diagnostic, le pronostic et le traitement. Ces derniers fonctionnent actuellement avec des sources d'énergie externes. Ces biopiles utilisant les molécules présentes dans les fluides biologiques sont des dispositifs médicaux prometteurs. Le glucose, qui est abondamment disponible dans le corps, est à l’étude comme biocarburant permettant de produire de l’énergie. Les enzymes utilisées pour produire l'énergie à partir des produits biochimiques sont immobilisées sur des électrodes en or par des médiateurs redox. Cependant, la faible puissance actuellement disponible et la sensibilité des enzymes à l'environnement limitent leur application in vivo. Malgré des recherches intensives, de nombreux problèmes restent à résoudre, notamment l'amélioration de la puissance, de la stabilité et de la biocompatibilité des biopiles.La réaction à corps étranger et l'isolement du dispositif médical par la formation d'une capsule fibreuse peuvent d'une part dénaturer les enzymes et, d'autre part, entraver la diffusion des analytes et de l'oxygène. Le travail décrit dans cette thèse vise à protéger les biopiles fonctionnant à base de glucose. Afin de résoudre les problèmes mentionnés ci-dessus, les hydrogels, actuellement développés pour diverses applications telles que l'administration de médicaments, l'ingénierie tissulaire et les dispositifs médicaux, offrent des propriétés prometteuses en tant que matériaux de revêtement.La première partie de la thèse est centrée sur l'évaluation de différents hydrogels injectables de faible poids moléculaire, en analysant à la fois la gélification in vitro et in vivo, la cinétique de dégradation, la réaction à corps étranger et l'angiogenèse. Les hydrogels présentent une dégradation lente et une intégration tissulaire optimale. Une angiogenèse accrue a été observée en raison de la libération d'une molécule pro-angiogénique pendant la dégradation de l'hydrogel.Dans la seconde partie de la thèse, l'un des hydrogels étudiés a été utilisé pour recouvrir l'électrode en or : le choix de l'enzyme a été basé sur des études de stabilité in vitro. En parallèle, le processus de revêtement a été optimisé, à la fois pour son uniformité et son épaisseur. Même si un revêtement plus épais présente l’avantage de protéger l’électrode contre la réaction à corps étranger, il est nécessaire de limiter l’épaisseur afin de maintenir une diffusion efficace des analytes et de l’oxygène.Les expériences en cours décrites dans la dernière partie de la thèse sont axées sur l'optimisation de l'implantation chez le rat et la mesure de l'activité des biopiles. De plus, les électrodes ont été connectées à une antenne pour établir une communication sans fil ; en effet, cela permettrait une mesure non invasive de l'activité enzymatique.En conclusion, ces travaux ont permis d'identifier un hydrogel pouvant être utilisé pour revêtir les électrodes de biopiles. Le sous-produit libéré lors de la biodégradation favorise l'angiogenèse au voisinage du matériau. Grâce à ce revêtement, on peut donc s'attendre à un échange accru d'analytes et d'oxygène, préalable indispensable à l'activité enzymatique. / Miniature enzymatic biofuel cells hold great potential to power the future generation of implantable medical devices, which are currently working on external power sources used for diagnosis, prognosis and treatment. Enzymatic biofuel cells appear to be promising in harvesting the energy from biochemicals present in physiological body fluids. Glucose, which is abundantly available in the body, is being explored as a biofuel to harvest energy. The enzymes employed to harvest the energy from the biochemicals are electrically wired on gold electrodes by redox mediators. However, the limitation of insufficient power, and the sensitivity of the enzymes towards host environment restrict their in vivo application. Despite several attempts, numerous challenges remain to be addressed such as improved current density, increased stability, and biocompatibility of enzymatic biofuel cells.Foreign body reaction and isolation of the medical device by formation of a fibrous capsule may firstly denature the enzymes, and secondly hinder the diffusion of analytes and oxygen. The work described in this thesis aims at protecting glucose based biofuel cells. As a strategy for combatting the bottlenecks mentioned above, hydrogels, currently developed for various applications such as drug delivery, tissue engineering, and medical device, offer promising properties as coating materials.The first part of the thesis is focused on evaluating different low molecular weight injectable hydrogels by analysing both in vitro and in vivo gel formation, degradation kinetics, foreign body reaction and angiogenesis. The hydrogels exhibit slow degradation, and optimal tissue integration. Enhanced angiogenesis was observed due to a pro-angiogenic molecule released during hydrogel degradation.In the second part of the thesis, one of the studied hydrogels was used to coat the gold electrode functionalised with enzyme: the selection of the enzyme was based on in vitro stability studies. In parallel, the process of coating was optimised, both for uniformity and thickness. Although a thicker coating should protect the electrode against foreign body reaction, it was necessary to limit the thickness in order to maintain an efficient analyte and oxygen diffusion.Ongoing experiments described in the last part of the thesis are focused on the optimisation of implantation in rat and measurement of the biofuel cell activity. In addition, the electrodes were connected to an antenna for wireless communication; indeed, such a device would allow for a non-invasive measurement of enzyme activity.To conclude, this work allowed for the identification of a hydrogel that can be used to coat the electrodes of biofuel cells. The byproduct released during the biodegradation favours angiogenesis in the vicinity of the material. Thanks to this coating, we can therefore expect an enhanced exchange of analytes and oxygen, which is a prerequisite for enzyme activity.

Current prices and demand for petroleum hydrocabons have generated an increase of oil spills around the country and the world. Health and environmental impacts associated to these organic pollutants represent a huge concern for the general public, leading the public and private sector to develop new technologies and methods to minimize or eliminate those risks. Ex-Situ bioremediation through biopiles, as a main remediation technique to treat a wide range of hydrocarbons, has been a topic of considerable research interest over the last years. It provides an economical and environmental solution to restore the environment to background levels. Nevertheless, successful bioremediation under cold climate conditions is of considerable concern in countries like Canada, as low temperatures can delay the rate of bioremediation of oil hydrocarbons, thus limiting the operation of soil treatment facilities to certain times of the year. Recent research has found out that bioremediation could be conducted even at low or cold temperatures with larger periods of times. And even more, the addition of petroleum degrading microorganisms (bioaugmentation) and nutrients or biosurfactants (biostimulation) could enhance the process in some cases. In the present study, a comprehensive assessment of bioaugmentation and biostimulation strategies for ex-situ bioremediation of petroleum contaminated soil under cold climate conditions is proposed. Field scale biopiles were constructed and subjected to different concentrations of commercial microbial consortia and mature compost, as bioaugmentation and biostimulation strategies, in a soil treatment facility at Moose Creek, Ontario over a period of 94 days (November 2012 to February 2013). Assessment and comparison of the biodegradation rates of total petroleum hydrocarbons (TPH) and their fractions were investigated. Furthermore, a response surface methodology (RSM) based on a factorial design to investigate and optimize the effects of the microbial consortia application rate and amount of compost on the TPH removal was also assessed. Results showed that biopiles inoculated with microbial consortia and amended with 10:1 soil to compost ratio under aerobic conditions performed the best, degrading 82% of total petroleum hydrocarbons (TPHs) with a first-order kinetic degradation rate of 0.016 d_1, under cold temperature conditions. The average removal efficiencies for TPHs after 94 days for control biopiles, with no amendments or with microbial consortia or compost only treatments were 48%, 55%, and 52%, respectively. Statistical analyses indicated a significant difference (p < 0.05) within and between the final measurements for TPHs and a significant difference between the treatment with combined effect, and the control biopiles. On the other hand, the modeling and optimization statistical analysis of the results showed that the microbial consortia application rate, compost amendment and their interactions have a significant effect on TPHs removal with a coefficient of determination (R2) of 0.88, indicating a high correlation between the observed and the predicted values for the model obtained. The optimum concentrations predicted via RSM were 4.1 ml m-3 for microbial consortia application rate, and 7% for compost amendment to obtain a maximum TPH removal of 90.7%. This research contributes to provide valuable knowledge to practitioners about cost-effective and existing strategies for ex-situ bioremediation under cold weather conditions.

Les biopiles représentent une solution attractive et ambitieuse pour développer des systèmes alternatifs de conversion d'énergie. Ce travail décrit la construction d'une biopile à éthanol/O2 (oxydation de l'éthanol à l'anode et réduction de l'oxygène à la cathode) avec des électrodes tridimensionnelles possédant une surface spécifique élevée. Le point de départ a été la fabrication et l'optimisation de bioélectrodes enzymatiques par immobilisation d'enzymes et de médiateurs sur des nanofibres de polyacrylonitrile, préparées par la méthode d'électrospinning, et recouvertes d'or. Ces bioélectrodes à base de nanofibres (biocathode et bioanode) ont été assemblées pour construire et caractériser une biopile à éthanol/O2 qui a fourni une densité de puissance de 1600 µW/cm2 par la méthode de polarisation et 210 µW/cm2 par imposition de résistances au système. Enfin, nous avons décrit la fabrication de la première biopile miniaturisée à éthanol/oxygène avec des enzymes immobilisées sur électrodes Au en s'appuyant sur les concepts de la microfluidique. La biopile microfluidique la plus performante a délivré 90 µW/cm2. Afin d'augmenter la puissance délivrée par ces systèmes miniaturisés, des résultats préliminaires ont été obtenus sur l'empilement en série ou en parallèle de biopiles fonctionnant avec des enzymes en solution. / Biofuel cells represent an attractive and ambitious option for developing alternative systems of energy conversion. This work describes the construction of an ethanol/O2 biofuel cell (ethanol oxidation at the anode and oxygen reduction oxygen at the cathode) from tridimensional electrodes with high specific surface area. The starting point was the synthesis and the optimization of the enzymatic bioelectrodes on gold electrodes by immobilizing enzymes and mediatorson polyacrylonitrile nanofibers, obtained by electrospinning method, and recovered by gold nanoparticles. The bioelectrodes (bioanode and biocathode) based on nanofibers have been assembled to build and to characterize an ethanol/O2 biofuel cell that has delivered a power density of 1600 µW/cm2 by the polarization method, and 210 µW/cm2 by imposing resistances to the system. Finally, we have described the production of the first miniaturized ethanol/O2 biofuel cell with immobilized enzymes at Au electrodes based on microfluidic concepts. The best microfluidic biofuel cell has delivered 90 µW/cm2. In order to increase the power delivered by these miniaturized systems, preliminary results have been obtained by stacking biofuel cells, working with enzymes in solution, in series or parallel.

Made available in DSpace on 2014-06-11T19:27:24Z (GMT). No. of bitstreams: 0 Previous issue date: 2005-08-18Bitstream added on 2014-06-13T20:16:40Z : No. of bitstreams: 1 morais_eb_me_rcla.pdf: 581837 bytes, checksum: 6b02ac6c5a3ca7b0528f8a1f3afc5d7e (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O potencial de um sistema de biopilhas em degradar resíduos oleosos provenientes de refinaria de petróleo também chamado de borra de óleo foi estudado, assim como a possibilidade de otimizar o mesmo através da bioestimulação (adição de fertilizantes) e bioenriquecimento (adição de inóculo). Primeiramente, verificou-se a biodegradabilidade do resíduo através do método respirométrico de Bartha, quantificando o CO2 emitido, observando os efeitos do uso de inóculo e de fertilizantes neste processo. Os microrganismos utilizados na produção do inóculo, fungos e bactérias, foram isolados de landfarming da Refinaria de Paulínia, REPLAN, estado de São Paulo, por serem adaptados ao ambiente de estresse ocasionado pelo resíduo oleoso e por terem demonstrado capacidade em biodegradar hidrocarbonetos de petróleo, em ensaios prévios realizados em laboratório. Foram construídas cinco biopilhas contendo solo poluído pela borra de óleo, nas constituições: 1 controle do experimento; 2 adicionada com inóculo; 3 com inóculo e fertilizante para plantas; 4 com inóculo e palha de arroz; 5 com inóculo, fertilizante e palha de arroz. Os resultados após 350 dias demonstraram redução da quantidade de resíduo em todas as biopilhas: 67%, 70%, 75%, 82% e 79% nas biopilhas 1, 2, 3, 4 e 5 respectivamente. As biopilhas contendo palha de arroz demonstraram degradação mais rápida do resíduo, principalmente nos dois primeiros meses deste estudo, provavelmente devido ao maior número de microrganismos que foram observados nas mesmas decorrente da adição do inóculo ou estimulação da microbiota natural. Nas condições de estudo, o inóculo adicionado nas biopilhas 2 e 3 não sobreviveram ao novo ambiente não influenciando a degradação do resíduo assim como a...

O potencial de um sistema de biopilhas em degradar resíduos oleosos provenientes de refinaria de petróleo também chamado de borra de óleo foi estudado, assim como a possibilidade de otimizar o mesmo através da bioestimulação (adição de fertilizantes) e bioenriquecimento (adição de inóculo). Primeiramente, verificou-se a biodegradabilidade do resíduo através do método respirométrico de Bartha, quantificando o CO2 emitido, observando os efeitos do uso de inóculo e de fertilizantes neste processo. Os microrganismos utilizados na produção do inóculo, fungos e bactérias, foram isolados de "landfarming" da Refinaria de Paulínia, REPLAN, estado de São Paulo, por serem adaptados ao ambiente de estresse ocasionado pelo resíduo oleoso e por terem demonstrado capacidade em biodegradar hidrocarbonetos de petróleo, em ensaios prévios realizados em laboratório. Foram construídas cinco biopilhas contendo solo poluído pela borra de óleo, nas constituições: 1 controle do experimento; 2 adicionada com inóculo; 3 com inóculo e fertilizante para plantas; 4 com inóculo e palha de arroz; 5 com inóculo, fertilizante e palha de arroz. Os resultados após 350 dias demonstraram redução da quantidade de resíduo em todas as biopilhas: 67%, 70%, 75%, 82% e 79% nas biopilhas 1, 2, 3, 4 e 5 respectivamente. As biopilhas contendo palha de arroz demonstraram degradação mais rápida do resíduo, principalmente nos dois primeiros meses deste estudo, provavelmente devido ao maior número de microrganismos que foram observados nas mesmas decorrente da adição do inóculo ou estimulação da microbiota natural. Nas condições de estudo, o inóculo adicionado nas biopilhas 2 e 3 não sobreviveram ao novo ambiente não influenciando a degradação do resíduo assim como a... (Resumo completo, clicar acesso eletrônico abaixo) / The potential of a biopile system to degradate oily residues from a petroleum refinery also called oil sludge was studied, as well as the possibility of its optimization through biostimulation (fertilizers addition) and bioaugmentation (inoculum addition). First, the biodegradability of the residue was verified through the Bartha flasks, quantifying the CO2 emitted, observing the effects of the inoculum and fertilizer use in this process. The microorganisms used in the inoculum production were isolated from the landfarming of Refinery of Paulínia, REPLAN, São Paulo State, as they are adapted to the environmental stress provoked by the oily residue showed the capacity to degradate petroleum hydrocarbons in previous assays in laboratory. Five biopiles were built with the soil polluted by the oil sludge, they were constituted by: 1 experimental control, 2 with inoculum; 3 with inoculum and plant fertilizer; 4 with inoculum and rice straw; 5 with inoculum, fertilizer and rice straw. The results after 350 days showed a reduction of the residue quantity in all the biopiles: 67%, 70%, 75%, 82% and 79% in the biopiles 1, 2, 3, 4 and 5 respectively. The biopiles containing rice straw showed a faster degradation of the residue mainly during the first two months of this study, probably due to the higher number of microorganisms provoked by the addition of the inoculum or stimulation natural microorganisms. At the conditions of this study, the addition of the inoculum to the biopiles 2 and 3 did not survive in the new environment not influencing the residue degradation, as well as the fertilizer addition did not have any influence to the biopiles 3 and 5. It was clear the importance of the addition of materials and aggregated such as the rice straw, to improve the soil characteristics regarding to aeration and permeability... (Complete abstract, access undermentioned electronic address) / Orientador: Sâmia Maria Tauk-Tornisielo / Coorientador: Ana Paula de Arruda Geraldes Kataoka / Banca: Ariovaldo José da Silva / Banca: Roberto Naves Domingos / Mestre