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This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Highlights of Research1. First Study to observe the influence of mitigating pH changes and its effect on laccase activity in a microbial fuel cell (MFC).2. Decoupling pH and salinity in the cathode chamber of MFC.3. Correlation of laccase activity with performance of the system. Results show that using Nafion 117 membrane limits salinity and pH changes in the cathode (100 mM acetate buffer as catholyte) leading to prolonged laccase activity and faster AO7 decolourisation compared to using CMI7000 as a membrane; similarly automatic pH control in the cathode chamber was found to be better than using 200 mM acetate buffer.It is suggested that while pH control in the cathode chamber is important, it does not guarantee sustained laccase activity; that salinity increases affect the activity and could be mitigated using a cation selective membrane.

More than 80% of wastewater from industries is discharged into receiving water bodies without any pollution control. Microbial fuel cells (MFCs) are a promising technology for the simultaneous treatment of wastewater and electricity production. With regard to azo-dye containing wastewater (e.g., from textile manufacturing), the dye may be fed via the anode chamber containing electrochemically active bacteria or via the cathode chamber containing laccase enzyme as catalyst for oxygen reduction. This study investigated which of the two approaches is the best with regard to rate of decolourization of the dye (Acid orange 7), COD reduction and electricity production. The power density was higher for the MFC Dye Cathode (50 ± 4 mW m −2 , COD reduction 80.4 ± 1.2%) compared with 42.5 ± 2.6 mW m −2 (COD reduction 69 ± 2%) for MFC Dye Anode. The time required for decolourization was longer in the MFC Dye Anode (Shewanella oneidensis) where only 20% decolourization was obtained after 24 h compared to 80% for the MFC Dye Cathode. The anodic dye degradation products were unstable when exposed to air resulting in regaining of color. In case of degradation by laccase in the cathode chamber, the decolourization products were stable and simpler in chemical structure as determined by GC-MS. This work suggests that feeding azo dyes in cathode chambers of MFCs containing laccase is a better way of treating the dyes compared to the commonly used approach of feeding the dye in the anode chamber provided enzyme activity can be sustained.

Redox mediators could be used to improve the efficiency of microbial fuel cells (MFCs) by enhancing electron transfer rates and decreasing charge transfer resistance at electrodes. However, many artificial redox mediators are expensive and/or toxic. In this study, laccase enzyme was employed as a biocathode of MFCs in the presence of two natural redox mediators (syringaldehyde (Syr) and acetosyringone (As)), and for comparison, a commonly-used artificial mediator 2,2 -azinobis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) was used to investigate their influence on azo dye decolorization and power production. The redox properties of the mediator-laccase systems were studied by cyclic voltammetry. The presence of ABTS and As increased power density from 54.7 ± 3.5 mW m −2 (control) to 77.2 ± 4.2 mW m −2 and 62.5 ± 3.7 mW m −2 respectively. The power decreased to 23.2 ± 2.1 mW m −2 for laccase with Syr. The cathodic decolorization of Acid orange 7 (AO7) by laccase indicated a 12-16% increase in decolorization efficiency with addition of mediators; and the Laccase-Acetosyringone system was the fastest, with 94% of original dye (100 mgL −1 ) decolorized within 24 h. Electrochemical analysis to determine the redox properties of the mediators revealed that syringaldehyde did not produce any redox peaks, inferring that it was oxidized by laccase to other products, making it unavailable as a mediator, while acetosyringone and ABTS revealed two redox couples demonstrating the redox mediator properties of these compounds. Thus, acetosyringone served as an efficient natural redox mediator for laccase, aiding in increasing the rate of dye decolorization and power production in MFCs. Taken together, the results suggest that natural laccase redox mediators could have the potential to improve dye decolorization and power density in microbial fuel cells. Energies 2018, 11, 3455 2 of 12The enzyme is widely utilised in the oxidation of phenolic and non-phenolic substrates such as dyes, pesticides, antibiotics etc.The redox potential of the substrate should be lower than that of laccase for oxidation to be thermodynamically feasible. The redox potential range for fungal laccase is between 0.4-0.8 V vs. standard hydrogen electrode (SHE), which is suitable for oxidation of phenolic substrates; for non-phenolic substrates that have a redox potential of >1.3 V vs. SHE, and cannot be oxidized directly by laccase, a redox mediator is required [5]. A redox mediator is a small molecular weight compound that is oxidized by the enzyme and reduced by the substrate continuously. They act as electron shuttles for large substrates that cannot access the active site of the enzyme, e.g., due to steric hindrance [6]. In laccase mediator systems (LMS), the enzyme oxidizes the mediators to form stable radicals with high redox potential that diffuse away from the enzyme active site and oxidize the substrates and get reduced in the process. In this way, laccase indirectly oxidises substrates that have high redox potentials or large molecular sizes [7] (...

Remediation of anthropogenic pollutants in our environment has become an imperative of the 21st century in order to sustain human activity and all life on the planet. With the current limitations of the existing technologies for this purpose, the need for innovative bioremediation technologies has become vitally important. Hitherto, electrochemically active microorganisms have only been a scientific curiosity and a platform for sustainable power production from waste material. However, recent research utilizing these electrochemically active microorganisms in bioelectrochemical systems (BES) has revealed their promising potential for bioremediation applications. The primary research focus of BES applications up-to now has been to optimize and increase their power output. The possibility of utilizing these systems for bioremediation applications has been a new facet of this field of work. This review provides a comprehensive outlook on the utilization of BES based technologies for remediation of xenobiotic environmental pollutants.

Microbial fuel cells (MFCs) produce electricity as a result of the microbial metabolism of organic substrates, hence they represent a sustainable approach for energy production and waste treatment. If the technology is to be implemented in industry, low cost and sustainable bioelectrodes must be developed to increase power output, increase waste treatment capacity, and improve service intervals. Although the current application of abiotic electrode catalysts, such as platinum and electrode binders such as Nafion leads to greater MFC performance, their use is cost prohibitive. Novel bioelectrodes which use cost effective and sustainable materials are being developed. These electrodes are developed with the intention to reduce start-up time, reduce costs, extend life-span and improve core MFC performance metrics (i.e. power density, current density, chemical oxygen demand (COD) reduction and Coulombic efficiency (CE)). Comparison of different MFC systems is not an easy task. This is due to variations in MFC design, construction, operation, and different inocula (in the case of mixed-culture MFCs). This high intra-system variability should be considered when assessing MFC data, operation and performance. This review article examines the major issues surrounding bioanode and biocathode improvement in different MFC systems, with the ultimate goal of streamlining and standardising improvement processes.

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