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)

Global increases in water demand and decreases in both the quantity and quality of fresh water resources have served as the major driving forces to develop sustainable use of water resources. One viable alternative is to explore non-traditional (impaired quality) water sources such as wastewater and seawater. The current paradigm for wastewater treatment is based on technologies that are energy intensive and fail to recover the potential resources (water and energy) in wastewater. Also, conventional desalination technologies like reverse osmosis (RO) are energy intensive. Therefore, there is a need for the development of sustainable wastewater treatment and desalination technologies for practical applications. Processes based on microbial electrochemical technologies (METs) such as microbial fuel cells (MFCs), microbial electrolysis cells (MECs) and microbial desalination cells (MDCs) hold promise for the treatment of wastewater with recovery of the inherent energy, and MDCs could be used for both desalination of seawater and energy recovery. METs use anaerobic bacteria, referred to as exoelectrogens, that are capable of transferring electrons exogenously to convert soluble organic matter present in the wastewater directly into an electrical current to produce electrical power (MFC and MDC) or biogas (MEC). In my dissertation, I investigated the three types of METs mentioned above to: 1) have a better insight on the effect of 4 oxygen intrusion on the microbial community structure and performance of air-cathode MFCs; 2) improve the desalination efficiency of air-cathode MDCs using ion exchange resins (IXRs); and 3) enrich for extremophilic exoelectrogens from the Red Sea brine pool using MECs. The findings from these studies can shape further research aimed at developing more efficient air-cathode MFCs for practical applications, a more efficient integrated IXRMDC configuration that can be used as a pre-treatment to RO, and exploring extreme environments as a source of extremophilic exoelectrogens for niche-specific applications of METs.

Increasing demand for freshwater and energy is pushing towards the development of alternative technologies that are sustainable. One of the realistic solutions to address this is utilization of the renewable resources like wastewater. Conventional wastewater treatment processes can be highly energy demanding and can fails to recover the full potential of useful resources such as energy in the wastewater. As a consequence, there is an urgent necessity for sustainable wastewater treatment technologies that could harness such resources present in wastewaters. Advanced treatment process based on microbial electrochemical technologies (METs) such as microbial fuel cells (MFCs) and microbial electrolysis cells (MECs) have a great potential for the resources recovery through a sustainable wastewater treatment process. METs rely on the abilities of microorganisms that are capable of transferring electrons extracellularly by oxidizing the organic matter in the wastewater and producing electrical current for electricity generation (MFC) or H2 and CH4 production (MEC). Propionate is an important volatile fatty acid (VFA) (24-70%) in some wastewaters and accumulation of this VFA can cause a process failure in a conventional anaerobic digestion (AD) system. To address this issue, MECs were explored as a novel, alternative wastewater treatment technology, with a focus on a better understanding of propionate oxidation in the anode of MECs. Having such knowledge could help in the development of more robust and efficient wastewater treatment systems to recover energy and produce high quality effluents. Several studies were conducted to: 1) determine the paths of electron flow in the anode of propionate fed MECs low (4.5 mM) and high (36 mM) propionate concentrations; 2) examine the effect of different set anode potentials on the electrochemical performance, propionate degradation, electron fluxes, and microbial community structure in MECs fed propionate; and 3) examine the temporal dynamics of microbial communities in MECs fed with low or high concentration of acetate or propionate relating to the reactor performance. Overall, the findings from these studies provides new knowledge on propionate oxidation in MECs. The discovery of such findings may shed light on the development of an energy positive wastewater treatment process capable of producing a high quality effluent.

In municipal wastewater treatment, anaerobic digestion is the slowest process requiring at least 15 day solids retention time (SRT). Treating only a small fraction of the total wastewater stream, anaerobic digesters require large reactor volumes and consistent heating (40°C). Thus, there is a growing need to investigate techniques to improve digestion efficiency. The long SRT requirement is a result of the time required for biological reactions such as hydrolysis and acetoclastic methanogenesis. There are numerous pretreatment methods which have so far been developed to particularly enhance hydrolysis. These pretreatment methods include thermalization, mechanical treatments, and chemical treatments. These methods aim to increase the degradability of the influent waste sludge which in turn will increase the efficiency of the digestion process. The goal of the research presented in this thesis is to enhance another limiting biological reaction: acetoclastic methanogenesis. Microbial electrolysis cell (MEC) technology was integrated into lab-scale anaerobic digesters in order to accelerate biosolids destruction under various SRT and temperature conditions. Various mathematical simulations were conducted using a developed steady-state ADM1 (Anaerobic Digestion Model No.1) model to further evaluate the performance of the digesters. The results of the research indicate that the proposed method is effective at shortened SRTs (e.g., 6 days) and can enhance the stability of anaerobic digestion when exposed to variations in temperature and influent composition. / Thesis / Master of Applied Science (MASc)

Heavy metal contamination in water is a serious environmental and human health issue. Lead (Pb2+) and cadmium (Cd2+) are strictly regulated in wastewater effluent due to their high toxicity at low concentrations. Heavy metals are difficult to remove in conventional biological wastewater treatment because they are water soluble and non-biodegradable. Advanced treatment, such as tight membrane filtration and ion exchange, can be applied but they often require a high electrical energy input and a large amount of chemicals for pre- or post-treatment. Microbial electrolysis cells (MECs) can be used to treat wastewater while simultaneously recovering energy in the form of hydrogen gas. Additionally, MECs were proven to be effective for heavy metal removal. The commonly investigated removal mechanism for heavy metals in MECs is reduction at the cathode where heavy metal ions are reduced to metallic solids. The research presented in this thesis examined the effectiveness of cathodic reduction and other heavy metal removal mechanisms in MECs over a wide range of metal concentrations (10 μg/L-12 mg/L). Lab-scale MEC operation demonstrated successful removal of both Pb2+ and Cd2+ under different electric conditions, operation times, and initial metal concentrations. In addition to cathodic reduction, heavy metal removal in MECs was demonstrated through chemical precipitation at the cathode and electrochemical reduction and biosorption at the bioanode. The results of this research also confirmed the importance of microbial activity at the bioanode to efficiently drive the removal mechanisms in MECs. / Thesis / Master of Applied Science (MASc)

Solid oxide cells are best known in the energy sector as novel power generation devices through solid oxide fuel cells (SOFCs), which enable the direct conversion of chemical energy to electrical energy and result in high efficiency power generation. However, solid oxide electrolysis cells (SOECs) are receiving increased attention as a hydrogen production technology through high temperature electrolysis applications. The development of higher fidelity methods for modeling transport phenomena within solid oxide cells is necessary for the advancement of these key technologies. The proposed thesis analyzes the increased transport path lengths caused by constriction resistance effects in prevalent solid oxide cell designs. Such effects are so named because they arise from reductions in active transport area. Constriction resistance effects of SOFC geometry on continuum level mass and electronic transport through SOFC anodes are simulated. These effects are explored via analytic solutions of the Laplace equation with model verification achieved by computational methods such as finite element analysis (FEA). Parametric studies of cell geometry and fuel stream composition are performed based upon the models developed. These studies reveal a competition of losses present between mass and electronic transport losses and demonstrate the benefits of smaller SOFC unit cell geometry. Furthermore, the models developed for SOFC transport phenomena are applied toward the analysis of SOECs. The resulting parametric studies demonstrate that geometric configurations that demonstrate enhanced performance within SOFC operation also demonstrate enhanced performance within SOEC operation. Secondarily, the electrochemical degradation of SOFCs is explored with respect to delamination cracking phenomena about and within the critical electrolyte-anode interface. For thin electrolytes, constriction resistance effects may lead to the loss of electro-active area at both anode-electrolyte and cathode-electrolyte interfaces. This effect (referred to as masking) results in regions of unutilized electrolyte cross-sectional area, which can be a critical performance hindrance. Again analytic and computational means are employed in analyzing such degradation issues.

This study mainly explores the development of alternative cathode materials for the electrochemical reduction of CO₂ by high temperature solid oxide electrolysis cells (HTSOECs), which operate in the reverse manner of solid oxide fuel cells (SOFCs). The conventional Ni-yttria stabilized zirconia (YSZ) cermets cathode suffered from coke formation, whereas the perovskite-type (La, Sr)(Cr, Mn)O₃ (LSCM) oxide material displayed excellent carbon resistance. Initial CO₂ electrolysis performance tests from different cathode materials prepared by screen-printing showed that LSCM based cathode performed poorer than Ni-YSZ cermets, due to non-optimized microstructure. Efforts were made on microstructure modification of LSCM based cathodes by means of various fabrication methods. Among the LSCM/YSZ graded cathode, extra catalyst (including Pd, Ni, CeO₂, and Pt) aided LSCM/GDC (Gd₀.₁Ce₀.₉O₁.₉₅) cathode, LSCM impregnated YSZ cathode, and GDC impregnated LSCM cathode, the GDC impregnated LSCM cathode, with porous LSCM as backbone for finely dispersed GDC nanoparticles, was found to possess the desired microstructure for CO₂ splitting reaction via SOEC. Incorporating of 0.5wt% Pd into GDC impregnated LSCM cathode gave rise to an Rp of 0.24 Ω cm² at open circuit voltage (OCV) at 900°C in CO₂-CO 70-30 mixture, comparable with the Ni/YSZ cermet cathode operated in the identical conditions. Meanwhile, the cathode kinetics and possible mechanisms of the electrochemical reduction of CO₂ were studied, and factors including CO₂/CO composition, operation temperature and potential were taken into account. The current-to-chemical efficiency of CO₂ electrolysis was evaluated with gas chromatography (GC). The high performance Pd and GDC co-impregnated LSCM cathode was also applied for CO₂ electrolysis without protective CO gas in feed. This cathode also displayed superb performance towards CO₂ electrochemical reduction under SOEC operation condition in CO₂/N₂ mixtures, though it had OCV as low as 0.12V at 900°C. The LSCM/GDC set of SOEC cathode materials were investigated in the application of steam electrolysis and H₂O-CO₂ co-electrolysis as well. For the former, adequate supply of steam was essential to avoid the appearance of S-shaped I-V curves and limited steam transport. The 0.5wt% Pd and GDC co-infiltrated LSCM material has been found to be a versatile cathode with high performance and good durability in SOEC operations.