Nitrogen Removal in Bioelectrochemical Systems

Abstract

Bioelectrochemical systems couple the oxidation of an electron donor at the anode with the reduction of an electron acceptor at the cathode, using microorganisms to catalyse one or both reactions. When the overall reaction is exergonic, a power output is generated and the system is referred to as microbial fuel cell (MFC); when power is added to the system and hydrogen is produced at the cathode through electrolysis of water, the system is referred to as microbial electrolysis cell (MEC). This PhD thesis is principally focused on the microbial fuel cells technology. Microbial fuel cells are regarded as a sustainable technology for electric energy generation from the oxidation of organic substrates contained in wastewater. The rising need for renewable energy sources and sanitation has encouraged intense research in this novel technology. Nevertheless, up untill now the interest has been primarily focused on the anodic oxidation of organic matter contained in wastewater. However, in addition to organics, wastewater also contains other pollutants, such as soluble nitrogen compounds, for which specific treatment is required. In conventional wastewater treatment systems, the organics available in the wastewater are typically used as electron donor during denitrification. However, a considerable fraction (>50%) of the chemical oxygen demand (COD) is still oxidized aerobically due to the large recirculation flows from the nitrification to the denitrification stages required in anoxic/aerobic configurations to allow for low nitrate levels in the final effluent. This increased COD demand is normally fulfilled by supplementary COD addition, with consequent increase of treatment costs. Alternatively, microorganisms can use inorganic carbon substrates and inorganic electron donors such as hydrogen for denitrification. However, the use of compressed hydrogen is hampered by its low solubility. As a solution, electrochemical hydrogen production permits in situ delivery of the electron donor and is advantaged by simplified control and dissolution of H2. The energy requirements to provide reducing power for denitrification can be decreased if bacteria use the electrode directly as electron donor without intermediate hydrogen production in bioelectrochemical systems. However, fundamental knowledge on bioelectrochemical denitrification is still lacking, therefore, this PhD thesis aims to fill some of these knowledge gaps and to solve some of the bottlenecks of the use of biocathodes. In particular, the goals of this work are: (i) to produce a suitable microbial community able to use the cathode as the sole electron donor during denitrification; (ii) to engineer a bioelectrochemical system able to couple the cathodic denitrification with the oxidation of organics at the anode; (iii) to characterize and quantify the electron losses during anodic and cathodic processes; (iv) to develop a bioelectrochemical system that maximises the nitrogen removal by integrating the nitrification stage into the cathode; finally, (v) to provide an insight into the structural properties of the biofilm performing nitrogen removal at the cathode. The results reveal that microbes can effectively utilize the electrode as electron donor for nitrate reduction to gaseous nitrogen at a redox potential that excludes intermediate production of hydrogen. Measurements revealed that acetoclastic methanogenesis and bacterial growth were responsible for causing the major electron losses at the anode. Adjusting the anodic potential did not achieve a significant overall reduction of the electron losses. At the cathode, the charge transfer efficiencies were instead very high, with the losses only due to the generation of nitrous oxide. Moreover, adjustments of the cathode potential resulted in higher efficiency. High carbon and nitrogen removal was obtained with a COD demand for denitrification as low as 2.4 g per g nitrogen denitrified, which is much lower than typically observed in heterotrophic–based nitrogen removal technologies (>7 g g 1). Nitrogen was removed at rates up to 0.256 kg N m-3 d-1, which is comparable to other autotrophic denitrification processes. Simultaneous nitrification and denitrification was observed in a combined system with cathodic aeration, at bulk dissolved oxygen (DO) levels up to 5 mg L-1, which is considerably higher than normally considered feasible for the process. Confocal laser scanning microscope analysis revealed the existence of a structured biofilm where putative nitrifying organisms occupied the outer layers in contact with the aerated bulk liquid, and putative denitrifying organisms occupy the layers closer to the electrode. These findings are significant in the field of bioelectrochemical systems as they help to unravel some of the complex questions relating to biocathodes. Additionally, the system provides an attractive option to achieve a very high level of nitrogen removal from wastewater with low COD/N ratios due to the selective utilisation of the COD for the denitrification reaction via the electrical transfer of reducing equivalents from the anode to the cathode. However, this research creates new questions, particularly regarding the mechanisms of electron transfer at the cathode. Also a number of practical design and optimisation challenges need to be overcome before wider applications can be considered