Heavy metals are a growing environmental concern as they are unable to be metabolized in the environment, leading to bioaccumulation in the food chain and impacting human health. Treating heavy metals is difficult and expensive. Current methods include precipitation (which generates sludge that is costly to dispose of) or requires the use of a membrane, which fouls and requires regeneration. Microbial electrolysis cells (MECs) represent an alternative for treating heavy metal contaminated wastewater. Reactor components are cheap, and operation requires only a small amount of electricity. The electrically active biofilm oxidizes organics in the wastewater while transferring electrons first to the anode, then to the cathode, where aqueous metals are reduced to a solid deposit, a mechanism called electrodeposition. Few studies have been conducted to investigate the best operational conditions for heavy metal removal in MECs. In this study, the effects of hydrodynamics, applied voltage, and initial metal concentration on heavy metal removal mechanisms are investigated, and the best operational practices are determined on a high level. Mixing in the cathode chamber increased electrodeposition by 15%, decreased the cathode potential by -0.06 V, and increased current generation between 10-30%. Increasing the applied voltage from 0.6 V to 1.2 V increased electrodeposition by 22%. With both mixing and higher voltage applied, 93.35% of cadmium was removed from the catholyte in 24 hours. Although high voltage application maximized electrodeposition for short-term treatment, long-term treatment indicated lower applied voltage resulted in healthier MEC reactors, better overall metal recoveries, along with a more stable cathode potential. / Thesis / Master of Applied Science (MASc)

Effective wastewater treatment is needed to reduce the water pollution problem. However, massive energy is consumed in wastewater treatment, required to design an innovative system to reduce the energy consumption to solve the energy crisis. Integrated photobioelectrochemical system (IPB) is a powerful system to combine microbial fuel cells (MFCs) and algal bioreactor together. This system has good performance on the organic degradation, removal of nitrogen and phosphorus, and recover the bioenergy via electricity generation and algal harvesting. This dissertation is divided to twelve chapters, about various aspects of the working mechanisms and actual application of IPB. Chapter 1 generally introduces the working mechanisms of MFCs, algal bioreactor, and modeling. Chapter 2 demonstrates the improvement of cathode material to improve the structure and catalytic performance to improve the MFC performance. Chapter 3 describes the process to use microbial electrolysis cell (MEC) to generate biohythane for the energy recovery. Chapters 4 and 5 demonstrate the application of stable isotope probing to study Shewanella oneidensis MR-1 in the MFCs. Chapters 6 to 8 describe the application of models to optimize MFC and IPB system performance. Chapter 9 describes the strategy improvement for the algal harvesting in IPB. Chapter 10 describes the application of scale-up bioelectrochemical systems on the long-term wastewater treatment. Chapter 11 finally concludes the perspectives of IPBs in the wastewater treatment and energy recovery. This dissertation comprehensively introduces IPB systems in the energy recovery and sustainable wastewater treatment in the future. / Ph. D. / The resource of pure water becomes more and more valuable, and the large discharge of the wastewater into the environment would even cause the environmental pollution. Thus, the wastewater is a necessary method to remove the organics out of the wastewater. However, the large energy consumption is a critical issue to solve due to the global energy burden. How to reduce the energy consumption in the wastewater treatment is the required step to achieve the sustainable water treatment. Integrated photobioelectrochemical system (IPB) is a new promising technology, alternative to the traditional wastewater treatment techniques (e.g., anaerobic digester or activated sludge reactor) with low energy consumption. The IPB system was to combine microbial fuel cells (MFCs), which is a typical bioelectrochemical system (BES), and the algal bioreactor together, to achieve the performance on the organic degradation, removal of nitrogen and phosphorus in the wastewater, and recover the bioenergy via electricity generation and algal harvesting. The system was proved to be effective, but most of the IPB systems were only proved to work in the laboratories, and there is still a large potential space to improve the IPB system performance in the actual environment. Herein, this dissertation combines multiple studies about the IPB improvement and scaled-up process in the real wastewater treatment. Chapter 1 generally introduces what are MFCs, algal bioreactor and modeling simulations. Chapter 2 demonstrates the method about how to improve the MFC material to enhance the treatment performance for better MFC performance. Chapter 3 describes how to use BES to convert the organics to the renewable gas (e.g., H₂ and CH₄) to recover the energy. Chapters 4 and 5 demonstrate the application of stable isotope probing to study the microbial behavior in the MFC. Chapters 6 to 8 describe the applications of model simulations to optimize MFC and IPB performance. Chapter 9 describes the new reactor to improve the algal harvesting process to obtain more energy from the IPB system. Chapter 10 describes how to use the scale-up IPB system to treat the real wastewater treatment. Chapter 11 finally puts forward some perspectives of IPBs in the wastewater treatment and energy recovery. This dissertation comprehensively gives a big picture about the development of IPB systems in the energy recovery and sustainable wastewater treatment in the future.

Bioelectrochemical systems (BES) is a platform technology that is able to realize versatile engineering functions and recover valuable resources in an energy-efficient manner. One of the potential applications of BES is to remove and recover nutrients simultaneously from nutrient-rich wastewater, such as digested manure from livestock. A four-chamber BES was developed and used in this study to explore the potential to remove and recover hexavalent Chromium from synthetic wastewater, and ammonia and phosphate from digested manure. The BES was able to achieve 99.6% removal of Chromium by membrane adsorption in 5 days but failed to recover in the concentration chamber. Nutrients were removed from the waste stream and recovered in the recirculated catholyte by the electrical field generated from the waste. The BES was demonstrated to achieve substantial COD removal, nutrients removal and recovery. On average, the removal efficiencies were about 50% for COD, 85% for NH4-N and 40% for PO4-P, and the concentration of NH4-N recovered in the catholyte was 670 mg/L after 5 cycles under an applied voltage of 0.8 V. PO4-P was not recovered in solution, probably because it has precipitated under the alkaline condition together with Mg2+ and Ca2+ concentrated in the catholyte. It was also demonstrated that nutrients removal and recovery depended on the current generation and were mostly completed at high current. To sum up, the BES was proven to be an effective and sustainable approach to remove and recover nutrients from digested manure. / Master of Science

Wastewater treatment has developed as a mature technology over time. However, conventional wastewater treatment is a very energy-intensive process. Bioelectrochemical system (BES) is an emerging technology that can treat wastewater and also recover resources such as energy in the form of electricity/hydrogen gas and nutrients such as nitrogen and phosphorus compounds. Microbial electrolysis cell (MEC) is a type of BES that, in the presence of an additional voltage, can treat wastewater and generate hydrogen gas. This is a promising approach for wastewater treatment and value-added product generation, though it may not be sustainable in the long run, as it relies on fossil fuels to provide that additional energy. Thus, it is important to explore alternative renewable resources that can provide energy to power MEC. Waste heat is one such resource that has not been researched extensively, particularly at the low-temperature spectrum. This was utilized as a renewable resource by converting waste heat to electricity using a device called thermoelectric generator (TEG). TEG converted simulated waste heat from an anaerobic digester to power an MEC. The feasibility of TEG to act as a power source for an MEC was investigated and its performance compared to the external power source. Various cold sources were analyzed to characterize TEG performance. To explore this integrated TEG-MEC system further, a hydraulic connection was added between the two systems. Wastewater was used as a cold source for TEG and it was recirculated to the anode of the MEC. This system showed improved performance with both systems mutually benefitting each other. The operational parameters were analyzed for the optimization of the system. The integrated system could generate hydrogen at a rate of 0.36 ± 0.05 m3 m-3 d-1 for synthetic domestic wastewater treatment. For the practical application, it is necessary to estimate the cost and narrow the focus on the functions of the system. Techno-economic analysis was performed for MEC with cost estimation and net present value model to understand the economic viability of the technology. The application niche of the BES was described and directions for addressing the challenges towards a full-scale operation were discussed. The present system provides a sustainable method for wastewater treatment and resource recovery which can play an important role in human health, social and economic development and a strong ecosystem. / Doctor of Philosophy / An average person produces about 50-75 gallons of wastewater every day. In addition to the households, wastewater is generated from industries and agricultural practices. As the population increases, the quantity of wastewater production will inevitably increase. To keep our rivers and oceans clean and safe, it is essential to treat the wastewater before it is discharged to the water bodies. However, the conventional wastewater treatment is a very energy (and thus cost) intensive process. For low-income and developing parts of the world, it is difficult to adapt the technology everywhere in its present form. Furthermore, as the energy is provided mostly by fossil fuels, their limited reserves and harmful environmental effects make it critical to find alternative methods that can treat the wastewater at a much lower energy input. For a circular and sustainable economy, it is important to realize wastewater as a resource which can provide us energy, nutrients, and water, rather than discard it as a waste. Bioelectrochemical systems (BES) is an emerging technology that can simultaneously treat wastewater and recover resources in the form of electricity/hydrogen gas, and nitrogen and phosphorus compounds. Microbial electrolysis cell (MEC) is a type of BES that is used to treat wastewater and generate hydrogen gas. An additional voltage is supplied to the MEC for producing hydrogen. In the long run, this may not be sustainable as it relies on fossil fuels to provide that additional energy. Thus, it is important to explore alternative renewable resources that can provide energy to power MEC. Waste heat is a byproduct of many industrial processes and widely available. This was utilized as a renewable resource by converting waste heat to electricity using a device called thermoelectric generator (TEG). TEG converted simulated waste heat from an anaerobic digester to power an MEC. The mutual benefit for MEC and TEG was also explored by connecting the system electrically and hydraulically. Cost-estimation of the system was performed to understand the economic viability and functions of the system were developed. The present system provides a sustainable method for wastewater treatment and resource recovery which can play an important role in human health, social and economic development and a strong ecosystem.

O nitrato nas águas subterrâneas é considerado um dos principais problemas com relação aos padrões de potabilidade estabelecidos pela Portaria MS nº 2914/2011, o limite é de 10 mg NNO3-/L, tendo em vista que a ingestão de altas concentrações de nitrato está associada a doenças como câncer e a metahemoglobinemia. As preocupações com o nitrato devem-se as concentrações insidiosas e persistentes deste íon registradas pela CETESB desde o início do monitoramento das águas subterrâneas em 1990. O presente trabalho propôs a avaliação de um processo alternativo para remoção de nitrato, trata-se de um sistema bioeletroquímico, também conhecido como MFC (Microbial Fuel Cells), que utiliza microrganismos para desnitrificação. Esse tratamento consiste no uso de processos biológicos potencializados pelo processo de eletrólise, aproveitando desta forma, os principais pontos característicos de cada processo de maneira combinada. O sistema foi testado em escala de bancada, e consiste basicamente em uma câmara anódica onde ocorre a oxidação da matéria orgânica e uma câmara catódica onde ocorre o processo de redução do nitrato a N2. Entre as câmaras é utilizada uma membrana de troca iônica de forma a permitir somente a passagem de prótons da câmara anódica para a catódica, além de impedir a difusão de oxigênio para a câmara catódica. O experimento realizou 8 testes variando a taxa de aplicação total de 2,88 a 11,52 L/dia com uma concentração 15 mg N-NO3-/L. Nos últimos dois testes ainda foi aplicada uma tensão externa. O sistema atingiu uma eficiência média de remoção de nitrato de 80,84 ± 16,73 %. As concentrações finais de nitrato permaneceram dentro dos padrões de potabilidade, com valor médio de 1,88 ± 2,03 mg N-NO3-/L, obtendo-se uma taxa de desnitrificação de 0,0498 ± 0,03 kg/m³.dia. O acúmulo de nitrito no sistema teve valor médio de 0,36 ± 0,37 mg N-NO2-/L. / Nitrate in groundwater is considered to be one of the main problems with regard to the potability standards established by Ordinance MS nº 2914/2011, the limit is 10 mg N-NO3-/L, considering that the intake of high concentrations of nitrate Is associated with diseases such as cancer and methemoglobinemia. Concerns with nitrate are due to the insidious and persistent concentrations of this ion recorded by CETESB since the beginning of groundwater monitoring in 1990. The present work proposed the evaluation of an alternative process for nitrate removal. This is a bioelectrochemical system, also known as MFC (Microbial Fuel Cells), which uses microorganisms for denitrification. This treatment consists in the use of biological processes potentiated by the electrolysis process, thus taking advantage of the main characteristic points of each process in a combined manner. The system was tested on a bench scale, and basically consists of an anodic chamber where the oxidation of organic matter occurs and a cathodic chamber where the process of nitrate reduction to N2 occurs. Between the chambers an ion exchange membrane is used in order to allow only the passage of protons from the anode chamber to the cathodic, in addition to preventing the diffusion of oxygen to the cathodic chamber. The experiment performed 8 tests varying the total application rate from 2.88 to 11.52 L/d with a concentration of 15 mg N-NO3-/L. In the last two tests an external voltage was still applied. The system achieved an average nitrate removal efficiency of 80.84 ± 16.73%. The final concentrations of nitrate remained within the potability standards, with an average value of 1.88 ± 2.03 mg N-NO3-/L, obtaining a denitrification rate of 0.0498 ± 0.03 kg/m³.d. The accumulation of nitrite in the system had an average value of 0.36 ± 0.37 mg N-NO2-/L.

The aims of this project were to investigate a range of limitations affecting the electrical performance of bioelectrochemical systems (BES) and their use as analytical tools. The model cyanobacterium Synechocystis sp. PCC6803 was used to characterize light-driven BESs, or biophotovoltaic (BPV) devices. The phycobilisome (PBS) antenna size was altered to modify light absorption. At low to medium light intensities the optimum PBS antenna size was found to consist of one phycocyanin (PC) disc. Incorporating pulsed amplitude fluorescence (PAM) measurements into the BPV characterization allowed simultaneous comparison of photosynthetic efficiency to EET in Synechocystis. Non-photochemical quenching (NPQ) was investigated as a limiting factor in biophotovoltaic efficiency and was found to be reduced in the PBS antenna-truncated mutants. Fluorescence and electrochemical data were combined to develop a framework for quantifying the efficiency of light to bioelectricity conversion. This approach is a first step towards a more comprehensive and detailed set of analytical tools to monitor EET in direct relation to the underlying photosynthetic biology. A set of metabolic electron sinks were deleted to remove a selection of pathways that might compete with extracellular electron transfer (EET). The combined deletion of a bi-directional hydrogenase - HoxH, nitric oxide reductase - NorB, cytochrome-c oxidase - COX, bd-quinol oxidase - cyd, and the respiratory terminal oxidase - ARTO, roughly doubled light driven electron flux to EET. Deletion of nitrate reductase - NarB, and nitrite reductase - NirA, increased EET to a similar degree, but combination with the other knockouts compromised cell viability and did not increase output further. In addition to Synechocystis, the purple non-sulphur α-proteobacterium Rhodopseudomonas palustris CGA009 was used to test the effect of storage molecule synthesis knockout in a more industrially relevant organic carbon source driven BES, or microbial fuel cell (MFC). However, the removal of glycogen and poly-ß-hydroxybutyrate (PHB) did not have a significant effect on electrical output. Finally, the importance of electrode material and design for cell to anode connections in an MFC was investigated. EET from R. palustris was greatly enhanced using custom designed graphene and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) aerogels. Pristine graphene is also shown for the first time to be a viable, low cost alternative to platinum as a cathodic catalyst. Together, these results present a holistic view of major limitations on electrical output from BESs that may contribute to enhancing EET for power generation from MFCs in the long term, and optimization of BPV devices as reliable analytical tools in the short term.

O nitrato nas águas subterrâneas é considerado um dos principais problemas com relação aos padrões de potabilidade estabelecidos pela Portaria MS nº 2914/2011, o limite é de 10 mg NNO3-/L, tendo em vista que a ingestão de altas concentrações de nitrato está associada a doenças como câncer e a metahemoglobinemia. As preocupações com o nitrato devem-se as concentrações insidiosas e persistentes deste íon registradas pela CETESB desde o início do monitoramento das águas subterrâneas em 1990. O presente trabalho propôs a avaliação de um processo alternativo para remoção de nitrato, trata-se de um sistema bioeletroquímico, também conhecido como MFC (Microbial Fuel Cells), que utiliza microrganismos para desnitrificação. Esse tratamento consiste no uso de processos biológicos potencializados pelo processo de eletrólise, aproveitando desta forma, os principais pontos característicos de cada processo de maneira combinada. O sistema foi testado em escala de bancada, e consiste basicamente em uma câmara anódica onde ocorre a oxidação da matéria orgânica e uma câmara catódica onde ocorre o processo de redução do nitrato a N2. Entre as câmaras é utilizada uma membrana de troca iônica de forma a permitir somente a passagem de prótons da câmara anódica para a catódica, além de impedir a difusão de oxigênio para a câmara catódica. O experimento realizou 8 testes variando a taxa de aplicação total de 2,88 a 11,52 L/dia com uma concentração 15 mg N-NO3-/L. Nos últimos dois testes ainda foi aplicada uma tensão externa. O sistema atingiu uma eficiência média de remoção de nitrato de 80,84 ± 16,73 %. As concentrações finais de nitrato permaneceram dentro dos padrões de potabilidade, com valor médio de 1,88 ± 2,03 mg N-NO3-/L, obtendo-se uma taxa de desnitrificação de 0,0498 ± 0,03 kg/m³.dia. O acúmulo de nitrito no sistema teve valor médio de 0,36 ± 0,37 mg N-NO2-/L. / Nitrate in groundwater is considered to be one of the main problems with regard to the potability standards established by Ordinance MS nº 2914/2011, the limit is 10 mg N-NO3-/L, considering that the intake of high concentrations of nitrate Is associated with diseases such as cancer and methemoglobinemia. Concerns with nitrate are due to the insidious and persistent concentrations of this ion recorded by CETESB since the beginning of groundwater monitoring in 1990. The present work proposed the evaluation of an alternative process for nitrate removal. This is a bioelectrochemical system, also known as MFC (Microbial Fuel Cells), which uses microorganisms for denitrification. This treatment consists in the use of biological processes potentiated by the electrolysis process, thus taking advantage of the main characteristic points of each process in a combined manner. The system was tested on a bench scale, and basically consists of an anodic chamber where the oxidation of organic matter occurs and a cathodic chamber where the process of nitrate reduction to N2 occurs. Between the chambers an ion exchange membrane is used in order to allow only the passage of protons from the anode chamber to the cathodic, in addition to preventing the diffusion of oxygen to the cathodic chamber. The experiment performed 8 tests varying the total application rate from 2.88 to 11.52 L/d with a concentration of 15 mg N-NO3-/L. In the last two tests an external voltage was still applied. The system achieved an average nitrate removal efficiency of 80.84 ± 16.73%. The final concentrations of nitrate remained within the potability standards, with an average value of 1.88 ± 2.03 mg N-NO3-/L, obtaining a denitrification rate of 0.0498 ± 0.03 kg/m³.d. The accumulation of nitrite in the system had an average value of 0.36 ± 0.37 mg N-NO2-/L.

Neste trabalho avaliou-se a influência das condições operacionais da célula a combustível microbiana (CCM) na remoção de matéria orgânica de águas residuárias e na geração de energia elétrica direta. As Hipóteses 1, 2 e 3 verificaram respectivamente as influências do tempo de detenção hidráulica (TDH), das condições mesofílica (25 ºC) e termofílica (55 ºC) de temperatura e da razão de recirculação (R) do efluente no cátodo da CCM (0, 1, 3 e 5) na geração de energia elétrica, na adesão e na comunidade microbiana e na remoção de DQO em CCM sem membrana de íon seletiva alimentada com água residuária sintética a base de sacarose. As Hipóteses 1, 2 e 3 foram aceitas. A redução do TDH permitiu maior geração de energia e dominância na comunidade microbiana e menor adesão da comunidade microbiana ao eletrodo. Enquanto que longos TDH removeram mais DQO, porém geraram menores valores de tensão elétrica. As condições termofílicas apresentaram maiores valores de tensão elétrica gerada e maior dominância da comunidade microbiana e menor adesão microbiana ao eletrodo e eficiência de remoção de DQO. A constante cinética aparente em condição termofílica ( 0,035 h-1) foi duas vezes menor que em condição mesofílica ( 0,083 h-1). O aumento da R melhorou a geração de energia e a remoção de DQO, pois houve melhor transferência de massa do meio líquido para os microrganismos e do meio gasoso para liquido e menor concentração de biomassa aderida ao eletrodo do cátodo aumentando a tensão elétrica gerada. Na Hipótese 4, verificou-se o uso e o efeito do TDH no tratamento de vinhaça de cana de açúcar em CCM sem membrana trocadora de íon seletivo operada em condição termofílica. A CCM foi capaz de remover a matéria orgânica da vinhaça de cana de açúcar e gerar energia elétrica direta, validando a Hipótese 4. As hipóteses 5, 6 e 7 avaliaram as influências da relação DQO, nitrogênio e fósforo da água residuária de produção de vinho, do tempo de retenção celular (TRC) e da configuração do eletrodo no desempenho de CCM de duas câmaras usando membrana de íon seletivo. Acataram-se as hipóteses 5, 6 e 7. O desbalanceamento entre DQO, nitrogênio e fósforo da água residuária de produção de vinho é um dos principais obstáculos para o uso desta tecnologia e a relação de DQO:N:P de 700:10:1 tem elevado potencial para gerar energia elétrica direta em CCM, embora não seja eficiente na remoção de matéria orgânica. A geração de energia aumenta com a redução do TRC, visto que há seleção dos microrganismos eletrogênicos e aumento da carga orgânica volumétrica específica reduzindo a competição por substrato. Entretanto, o TRC não influenciou a remoção de matéria orgânica, pois somente uma pequena parte da DQO foi removida similar em todos os TRC. As características físicas do eletrodo como a porosidade, a rugosidade e a densidade de área do eletrodo e a biocompatibilidade do eletrodo são fatores determinantes para aumentar o desempenho da CCM. Entre os eletrodos estudados, o feltro de carbono foi o melhor material encontrado. / In this work the influence of the operational conditions of the microbial fuel cell (MFC) were evaluated in organic matter removal from wastewater treatment and in the power generation. Hypotheses 1, 2 and 3 respectively checked the influences of hydraulic retention time (HRT), of mesophilic and thermophilic conditions (25 °C and 55 °C, respectively) and the recirculation ratio (R) of the effluent in cathode of MFC (0, 1, 3 and 5) in the power generation, microbial adhesion and community and COD removal of membraneless MFC fed with synthetic wastewater based on sucrose. Hypotheses 1, 2 and 3 have been accepted. Reducing the HRT increased the power generation and the dominance in microbial community and decreased the COD removal efficiency and microbial adhesion to the electrode. Long HRT more efficiently removed the organic matter but generated lower voltages. The thermophilic conditions yielded a more dominant microbial community that favored power generation compared with the mesophilic conditions because of reduced microbial adhesion to the electrode. The COD removal efficiencies were higher under mesophilic conditions than under thermophilic conditions due to the higher apparent kinetic constant at mesophilic conditions (0.083 h-1) than in thermophilic conditions (0.035 h-1). Increasing the R improved the power generation and the COD removal, because the mass transfer in the liquid medium for microorganisms was improved and the biomass adhered to the cathode electrode decreased increasing the voltage. In Hypothesis 4, the use and effect of HRT in treating sugar cane vinasse in membraneless MFC operated at thermophilic conditions were evaluated. The CCM was able to remove the COD of sugarcane vinasse and generate electricity directly, confirming the hypothesis 4. Hypotheses 5, 6 and 7 assessed the influences of COD, nitrogen and phosphorus ratio in winery wastewater, of sludge retention time (SRT) and of electrode configuration in dual chamber MFC. Hypotheses 5, 6 and 7 were adopted. The misbalance between COD, nitrogen and phosphorus from winery wastewater is a major obstacle to the use of this technology and COD:N:P ratio of 700:10:1 had high potential to generate power in MFC, although it is not effective in removing organic matter. The power generation increases with the reduction of the SRT, since there were the selection of bioeletrogenic microorganisms and increased the volumetric organic load rate reducing competition for substrate. However, the SRT did not affect the removal of organic matter, because only a small part of COD was removed regardless of SRT. Physical characteristics of the electrode as porosity, roughness and the electrode area density and the biocompatibility of the electrode are key factors to increase the performance of CCM. The carbon felt was the best studied material having the highest values of porosity, roughness and the electrode area density.

De multiples micro-organismes ont la capacité de catalyser l’oxydation électrochimique de matières organiques en s’organisant en biofilm à la surface d’anodes. Ce processus est à la base de procédés électro-microbiens très innovants tels que les piles à combustible microbiennes ou les électrolyseurs microbiens. L’interface biofilm/électrode a été l’objet de nombreuses étudesdont les conclusions restent difficiles à démêler en partie du fait de la diversité des paramètres interfaciaux mis en jeu. L’objet de ce travail de thèse est d’exploiter les technologies microsystèmes pour focaliser l’impact de la topographie de surface des électrodes sur le développement du biofilm et sur ses performances électro-catalytiques. La formation de biofilmsélectroactifs de Geobacter sulfurreducens a été étudiée sur des électrodes d’or présentant des topographies bien contrôlées, sous la forme de rugosité, porosité, réseau de piliers, à des échellesallant du nanomètre à quelques centaines de micromètres. La présence de microrugosité a permis d’accroitre les densités de courant d’un facteur 8 par rapport à une surface lisse et son effet a étéquantifié à l’aide du paramètre Sa. Nous avons tenté de distinguer les effets des différentes échelles de rugosité sur le développement du biofilm et la vitesse des transferts électroniques.L’intérêt de la microporosité a été discuté. L’accroissement de surface active par la présence de micro-piliers s’est avéré très efficace et une approche théorique a donné des clés de compréhension et d’optimisation. Les connaissances acquises dans les conditions de culture pure ont finalement été confrontées avec la mise en oeuvre de biofilms multi-espèces issus d’un inoculum complexe provenant de sédiments marins. / Many microorganisms have the ability to catalyze the electrochemical oxidation of organic matterby self-organizing into biofilm on the surface of anodes. This process is the basis of highlyinnovative electro-microbial processes such as microbial fuel cells or microbial electrolysis cells.The biofilm/electrode interface has been the subject of numerous studies whose conclusionsremain difficult to disentangle partly because of the diversity of the interfacial parameters involved.The purpose of this thesis work is to exploit microsystem technologies to focus the impact ofelectrode surface topography on biofilm development and electro-catalytic performance. Theformation of electroactive biofilms of Geobacter sulfurreducens was studied on gold electrodespresenting well-controlled topographies, in the form of roughness, porosity, pillar networks, atscales ranging from nanometer to a few hundred micrometers. The presence of micro-roughnessincreased the current densities by a factor of 8 compared to a smooth surface and its effect wasquantified using the Sa parameter. We have tried to distinguish the effects of different roughnessscales on biofilm development and electron transfer rates. The suitability of micro-porosity wasdiscussed. The increase of active surface area by the presence of micro-pillars has proved veryeffective and a theoretical approach has given keys to understanding and optimization. Theknowledge acquired under pure culture conditions was finally confronted with the use of multispeciesbiofilms formed from a complex inoculum coming from marine sediments.

Neste trabalho avaliou-se a influência das condições operacionais da célula a combustível microbiana (CCM) na remoção de matéria orgânica de águas residuárias e na geração de energia elétrica direta. As Hipóteses 1, 2 e 3 verificaram respectivamente as influências do tempo de detenção hidráulica (TDH), das condições mesofílica (25 ºC) e termofílica (55 ºC) de temperatura e da razão de recirculação (R) do efluente no cátodo da CCM (0, 1, 3 e 5) na geração de energia elétrica, na adesão e na comunidade microbiana e na remoção de DQO em CCM sem membrana de íon seletiva alimentada com água residuária sintética a base de sacarose. As Hipóteses 1, 2 e 3 foram aceitas. A redução do TDH permitiu maior geração de energia e dominância na comunidade microbiana e menor adesão da comunidade microbiana ao eletrodo. Enquanto que longos TDH removeram mais DQO, porém geraram menores valores de tensão elétrica. As condições termofílicas apresentaram maiores valores de tensão elétrica gerada e maior dominância da comunidade microbiana e menor adesão microbiana ao eletrodo e eficiência de remoção de DQO. A constante cinética aparente em condição termofílica ( 0,035 h-1) foi duas vezes menor que em condição mesofílica ( 0,083 h-1). O aumento da R melhorou a geração de energia e a remoção de DQO, pois houve melhor transferência de massa do meio líquido para os microrganismos e do meio gasoso para liquido e menor concentração de biomassa aderida ao eletrodo do cátodo aumentando a tensão elétrica gerada. Na Hipótese 4, verificou-se o uso e o efeito do TDH no tratamento de vinhaça de cana de açúcar em CCM sem membrana trocadora de íon seletivo operada em condição termofílica. A CCM foi capaz de remover a matéria orgânica da vinhaça de cana de açúcar e gerar energia elétrica direta, validando a Hipótese 4. As hipóteses 5, 6 e 7 avaliaram as influências da relação DQO, nitrogênio e fósforo da água residuária de produção de vinho, do tempo de retenção celular (TRC) e da configuração do eletrodo no desempenho de CCM de duas câmaras usando membrana de íon seletivo. Acataram-se as hipóteses 5, 6 e 7. O desbalanceamento entre DQO, nitrogênio e fósforo da água residuária de produção de vinho é um dos principais obstáculos para o uso desta tecnologia e a relação de DQO:N:P de 700:10:1 tem elevado potencial para gerar energia elétrica direta em CCM, embora não seja eficiente na remoção de matéria orgânica. A geração de energia aumenta com a redução do TRC, visto que há seleção dos microrganismos eletrogênicos e aumento da carga orgânica volumétrica específica reduzindo a competição por substrato. Entretanto, o TRC não influenciou a remoção de matéria orgânica, pois somente uma pequena parte da DQO foi removida similar em todos os TRC. As características físicas do eletrodo como a porosidade, a rugosidade e a densidade de área do eletrodo e a biocompatibilidade do eletrodo são fatores determinantes para aumentar o desempenho da CCM. Entre os eletrodos estudados, o feltro de carbono foi o melhor material encontrado. / In this work the influence of the operational conditions of the microbial fuel cell (MFC) were evaluated in organic matter removal from wastewater treatment and in the power generation. Hypotheses 1, 2 and 3 respectively checked the influences of hydraulic retention time (HRT), of mesophilic and thermophilic conditions (25 °C and 55 °C, respectively) and the recirculation ratio (R) of the effluent in cathode of MFC (0, 1, 3 and 5) in the power generation, microbial adhesion and community and COD removal of membraneless MFC fed with synthetic wastewater based on sucrose. Hypotheses 1, 2 and 3 have been accepted. Reducing the HRT increased the power generation and the dominance in microbial community and decreased the COD removal efficiency and microbial adhesion to the electrode. Long HRT more efficiently removed the organic matter but generated lower voltages. The thermophilic conditions yielded a more dominant microbial community that favored power generation compared with the mesophilic conditions because of reduced microbial adhesion to the electrode. The COD removal efficiencies were higher under mesophilic conditions than under thermophilic conditions due to the higher apparent kinetic constant at mesophilic conditions (0.083 h-1) than in thermophilic conditions (0.035 h-1). Increasing the R improved the power generation and the COD removal, because the mass transfer in the liquid medium for microorganisms was improved and the biomass adhered to the cathode electrode decreased increasing the voltage. In Hypothesis 4, the use and effect of HRT in treating sugar cane vinasse in membraneless MFC operated at thermophilic conditions were evaluated. The CCM was able to remove the COD of sugarcane vinasse and generate electricity directly, confirming the hypothesis 4. Hypotheses 5, 6 and 7 assessed the influences of COD, nitrogen and phosphorus ratio in winery wastewater, of sludge retention time (SRT) and of electrode configuration in dual chamber MFC. Hypotheses 5, 6 and 7 were adopted. The misbalance between COD, nitrogen and phosphorus from winery wastewater is a major obstacle to the use of this technology and COD:N:P ratio of 700:10:1 had high potential to generate power in MFC, although it is not effective in removing organic matter. The power generation increases with the reduction of the SRT, since there were the selection of bioeletrogenic microorganisms and increased the volumetric organic load rate reducing competition for substrate. However, the SRT did not affect the removal of organic matter, because only a small part of COD was removed regardless of SRT. Physical characteristics of the electrode as porosity, roughness and the electrode area density and the biocompatibility of the electrode are key factors to increase the performance of CCM. The carbon felt was the best studied material having the highest values of porosity, roughness and the electrode area density.