Assessment of the microbial electrochemical sensor (SENTRY™) as a potential wastewater quality monitoring tool for common pollutants found in Malaysia.

Bioelectrochemical sensors for environment monitoring have the potential to provide facility operators with real-time data, allowing for better and more timely decision-making regarding water and wastewater treatment. To assess the robustness and sensitivity of the Sentry™ biosensor in local conditions, it was tested in Malaysia using domestically available wastewater. The study objectives included (1) enrich the biosensor locally, (2) operate and test the biosensor with local domestic wastewater, and (3) determine the biosensor's responsiveness to model pollutants through pollutant spike and immersion test as well as response to absence of wastewater. Lab-scale operation shows the biosensor was successfully enriched with (1) local University Kebangsaan Malaysia's, microbial community strain collection and (2) local municipal wastewater microflora, operated for more than 50 days with a stable yet responsive carbon consumption rate (CCR) signal. Meanwhile, two independent biosensors were also enriched and operated in Indah Water Research Centre's crude sewage holding tank, showing a stable response to the wastewater. Next, a pilot scale setup was constructed to test the enriched biosensors for the spiked-pollutant test. The biosensors showed a proportional CCR response (pollutant presence detected) towards several organic compounds in the sewage, including ethanol, chicken blood, and dilution of tested sewage but less to curry powder, methanol, and isopropanol. Conversely, there was no significant response (pollutant presence not detected) towards hexane, Congo red, engine oil, and paint, which may be due to their non-biodegradability and/or insoluble nature. Additionally, the biosensors were exposed to air for 6 h to assess their robustness towards aerobic shock with a positive result. Overall, the study suggested that the biosensor could be a powerful monitoring tool, given its responsiveness towards organic compounds in sewage under normal conditions.

Rapid Surface Modification of Stainless Steel 304L Electrodes for Microbial Electrochemical Sensor Application.

Electrogenic microorganisms serve as important biocatalysts for microbial electrochemical sensors (MESes). The electrical signal produced is based on the rate of electron transfer between the microbes and electrodes, which represents the biotoxicity of water. However, existing MESes require complex and sophisticated fabrication methods. Here, several low-cost and rapid surface modification strategies (carbon powder-coated, flame-oxidized, and acid-bleached) have been demonstrated and studied for biosensing purposes. Surface-modified MESe bioanodes were successfully applied to detect multiple model pollutants including sodium acetate, ethanol, thinner, and palm oil mill effluent under three different testing sequences, namely, pollutant incremental, pollutant dumping, and water dilution tests. The carbon powder-coated bioanode showed the most responsive signal profile for all the three tests, which is in line with the average roughness values (Ra) when tested with atomic force microscopy. The carbon powder-coated electrode possessed a Ra value of 0.844, while flame-oxidized, acid-bleached, and control samples recorded 0.323, 0.336, and 0.264, respectively. The higher roughness was caused by the carbon coating and provided adhesive sites for microbial attachment and growth. The accuracy of MESe was also verified by correlating with chemical oxygen demand (COD) results. Similar to the sensitivity test, the carbon powder-coated bioanode obtained the highest R2 value of 0.9754 when correlated with COD results, indicating a high potential of replacing conventional water quality analysis methods. The reported work is of great significance to showcase facile surface modification techniques for MESes, which are cost-effective and sustainable while retaining the biocompatibility toward the microbial community with carbon-based coatings.

Role of microbial electrosynthesis system in CO2 capture and conversion: a recent advancement toward cathode development.

Microbial electrosynthesis (MES) is an emerging electrochemical technology currently being researched as a CO2 sequestration method to address climate change. MES can convert CO2 from pollution or waste materials into various carbon compounds with low energy requirements using electrogenic microbes as biocatalysts. However, the critical component in this technology, the cathode, still needs to perform more effectively than other conventional CO2 reduction methods because of poor selectivity, complex metabolism pathways of microbes, and high material cost. These characteristics lead to the weak interactions of microbes and cathode electrocatalytic activities. These approaches range from cathode modification using conventional engineering approaches to new fabrication methods. Aside from cathode development, the operating procedure also plays a critical function and strategy to optimize electrosynthesis production in reducing operating costs, such as hybridization and integration of MES. If this technology could be realized, it would offer a new way to utilize excess CO2 from industries and generate profitable commodities in the future to replace fossil fuel-derived products. In recent years, several potential approaches have been tested and studied to boost the capabilities of CO2-reducing bio-cathodes regarding surface morphology, current density, and biocompatibility, which would be further elaborated. This compilation aims to showcase that the achievements of MES have significantly improved and the future direction this is going with some recommendations. Highlights - MES approach in carbon sequestration using the biotic component.- The role of microbes as biocatalysts in MES and their metabolic pathways are discussed.- Methods and materials used to modify biocathode for enhancing CO2 reduction are presented.

Construction of microbial electrodialysis cells equipped with internal proton migration pathways: Enhancement of wastewater treatment, desalination, and hydrogen production.

Microbial electrodialysis cells (MEDCs) offer simultaneous wastewater treatment, water desalination, and hydrogen production. In a conventional design of MEDCs, the overall performance is retarded by the accumulation of protons on the anode due to the integration of an anion exchange membrane (AEM). The accumulation of protons reduces the anolyte pH to become acidic, affecting the microbial viability and thus limiting the charge carrier needed for the cathodic reaction. This study has modified the conventional MEDC with an internal proton migration pathway, known as the internal proton migration pathway-MEDC (IP-MEDC). Simulation tests under abiotic conditions demonstrated that the pH changes in the anolyte and catholyte of IP-MEDC were smaller than the pH changes in the anolyte and catholyte without the proton pathways. Under biotic conditions, the performance of the IP-MEDC agreed well with the simulation test, showing a significantly higher chemical oxygen demand (COD) removal rate, desalination rate, and hydrogen production than without the migration pathway. This result is supported by the lowest charge transfer resistance shown by EIS analysis and the abundance of microbes on the bioanode through field emission scanning electron microscopy (FESEM) observation. However, hydrogen production was diminished in the second-fed batch cycle, presumably due to the active diffusion of high Cl¯ concentrations from desalination to the anode chamber, which was detrimental to microbial growth. Enlarging the anode volume by threefold improved the COD removal rate and hydrogen production rate by 1.7- and 3.4-fold, respectively, owing to the dilution effect of Cl¯ in the anode. This implied that the dilution effect satisfies both the microbial viability and conductivity. This study also suggests that the anolyte and catholyte replacement frequencies can be reduced, typically at a prolonged hydraulic retention time, thus minimizing the operating cost (e.g., solution pumping). The use of a high concentration of NaCl (35 g L-1) in the desalination chamber and catholyte provides a condition that is close to practicality.

Enhancing hydrogen production through anode fed-batch mode and controlled cell voltage in a microbial electrolysis cell fully catalysed by microorganisms.

A microbial electrolysis cell (MEC) fully catalysed by microorganisms is an attractive technology because it incorporates the state-of-the-art concept of converting organic waste to hydrogen with less external energy input than conventional electrolysers. In this work, the impact of the anode feed mode on the production of hydrogen by the biocathode was studied. In the first part, three feed modes and MEC performance in terms of hydrogen production were evaluated. The results showed the highest hydrogen production under the continuous mode (14.6 ± 0.4), followed by the fed-batch (12.7 ± 0.4) and batch (0 L m-2 cathode day-1) modes. On one hand, the continuous mode only increased by 15% even though the hydraulic retention time (HRT) (2.78 h) was lower than the fed-batch mode (HRT 5 h). A total replacement (fed-batch) rather than a constant mix of existing anolyte and fresh medium (continuous) was preferable. On the other hand, no hydrogen was produced in batch mode due to the extensive HRT (24 h) and bioanode starvation. In the second part, the fed-batch mode was further evaluated using a chronoamperometry method under a range of applied cell voltages of 0.3-1.6 V. Based on the potential evolution at the electrodes, three main regions were identified depending on the applied cell voltages: the cathode activation (<0.8 V), transition (0.8-1.1 V), and anode limitation (>1.1 V) regions. The maximum hydrogen production recorded was 12.1 ± 2.1 L m-2 cathode day-1 at 1.0 V applied voltage when the oxidation and reduction reactions at the anode and cathode were optimal (2.38 ± 0.61 A m-2). Microbial community analysis of the biocathode revealed that Alpha-, and Deltaproteobacteria were dominant in the samples with >70% abundance. At the genus level, Desulfovibrio sp. was the most abundant in the samples, showing that these microbes may be responsible for hydrogen evolution.

Enhanced bio-production from CO2 by microbial electrosynthesis (MES) with continuous operational mode.

Technologies able to convert CO2 to various feedstocks for fuels and chemicals are emerging due to the urge of reducing greenhouse gas emissions and de-fossilizing chemical production. Microbial electrosynthesis (MES) has been shown a promising technique to synthesize organic products particularly acetate using microorganisms and electrons. However, the efficiency of the system is low. In this study, we demonstrated the simple yet efficient strategy in enhancing the efficiency of MES by applying continuous feeding regime. Compared to the fed-batch system, continuous operational mode provided better control of pH and constant medium refreshment, resulting in higher acetate production rate and more diverse bio-products, when the cathodic potential of -1.0 V Ag/AgCl and dissolved CO2 were provided. It was observed that hydraulic retention time (HRT) had a direct effect on the pattern of production, acetate production rate and coulombic efficiency. At HRT of 3 days, pH was around 5.2 and acetate was the dominant product with the highest production rate of 651.8 ± 214.2 ppm per day and a significant coulombic efficiency of 90%. However at the HRT of 7 days, pH was lower at around 4.5, and lower but stable acetate production rate of 280 ppm per day and a maximum coulombic efficiency of 80% was obtained. In addition, more diverse and longer chain products, such as butyrate, isovalerate and caproate, were detected with low concentrations only at the HRT of 7 days. Although microbial community analysis showed the change in the planktonic cells communities after switching the fed-batch mode to continuous feeding regime, Acetobacterium still remained as the responsible bacteria for CO2 reduction to acetate, dominating the cathodic biofilm.

Zinc removal and recovery from industrial wastewater with a microbial fuel cell: Experimental investigation and theoretical prediction.

Microbial fuel cells (MFCs) that simultaneously remove organic contaminants and recovering metals provide a potential route for industry to adopt clean technologies. In this work, two goals were set: to study the feasibility of zinc removal from industrial effluents using MFCs and to understand the removal process by using reaction rate models. The removal of Zn2+ in MFC was over 96% for synthetic and industrial samples with initial Zn2+ concentrations less than 2.0 mM after 22 h of operation. However, only 83 and 42% of the zinc recovered from synthetic and industrial samples, respectively, was attached on the cathode surface of the MFCs. The results marked the domination of electroprecipitation rather than the electrodeposition process in the industrial samples. Energy dispersive X-ray (EDX) analysis showed that the recovered compound contained not only Zn but also O, evidence that Zn(OH)2 could be formed. The removal of Zn2+ in the MFC followed a mechanism where oxygen was reduced to hydroxide before reacting with Zn2+. Nernst equations and rate law expressions were derived to understand the mechanism and used to estimate the Zn2+ concentration and removal efficiency. The zero-, first- and second-order rate equations successfully fitted the data, predicted the final Zn2+ removal efficiency, and suggested that possible mechanistic reactions occurred in the electrolysis cell (direct reduction), MFC (O2 reduction), and control (chemisorption) modes. The half-life, t1/2, of the Zn2+ removal reaction using synthetic and industrial samples was estimated to be 7.0 and 2.7 h, respectively. The t1/2 values of the controls (without the power input from the MFC bioanode) were much slower and were recorded as 21.5 and 7.3 h for synthetic and industrial samples, respectively. The study suggests that MFCs can act as a sustainable and environmentally friendly technology for heavy metal removal without electrical energy input or the addition of chemicals.

Pushing microbial desalination cells towards field application: Prevailing challenges, potential mitigation strategies, and future prospects.

Microbial desalination cells (MDCs) have been experimentally proven as a versatile bioelectrochemical system (BES). They have the potential to alleviate environmental pollution, reduce water scarcity and save energy and operational costs. However, MDCs alone are inadequate to realise a complete wastewater and desalination treatment at a high-efficiency performance. The assembly of identical MDC units that hydraulically and electrically connected can improve the performance better than standalone MDCs. In the same manner, the coupling of MDCs with other BES or conventional water reclamation technology has also exhibits a promising performance. However, the scaling-up effort has been slowly progressing, leading to a lack of knowledge for guiding MDC technology into practicality. Many challenges remain unsolved and should be mitigated before MDCs can be fully implemented in real applications. Here, we aim to provide a comprehensive chronological-based review that covers technological limitations and mitigation strategies, which have been developed for standalone MDCs. We extend our discussion on how assembled, coupled and scaled-up MDCs have improved in comparison with standalone and lab-scale MDC systems. This review also outlines the prevailing challenges and potential mitigation strategies for scaling-up based on large-scale specifications and evaluates the prospects of selected MDC systems to be integrated with conventional anaerobic digestion (AD) and reverse osmosis (RO). This review offers several recommendations to promote up-scaling studies guided by the pilot scale BES and existing water reclamation technologies.

Effects of Applied Potential and Reactants to Hydrogen-Producing Biocathode in a Microbial Electrolysis Cell.

Understanding the mechanism of electron transfer between the cathode and microorganisms in cathode biofilms in microbial electrolysis cells (MECs) for hydrogen production is important. In this study, biocathodes of MECs were successfully re-enriched and subjected to different operating parameters: applied potential, sulfate use and inorganic carbon consumption. It was hypothesized that biocathode catalytic activity would be affected by the applied potentials that initiate electron transfer. While inorganic carbon, in the form of bicarbonate, could be a main carbon source for biocathode growth, sulfate could be a terminal electron acceptor and thus reduced to elemental sulfurs. It was found that potentials more negative than -0.8 V (vs. standard hydrogen electrode) were required for hydrogen production by the biocathode. In additional, a maximum hydrogen production was observed at sulfate and bicarbonate concentrations of 288 and 610 mg/L respectively. Organic carbons were found in the cathode effluents, suggesting that microbial interactions probably happen between acetogens and sulfate reducing bacteria (SRB). The hydrogen-producing biocathode was sulfate-dependent and hydrogen production could be inhibited by excessive sulfate because more energy was directed to reduce sulfate (E° SO42- /H2S = -0.35 V) than proton (E° H+/H2 = -0.41 V). This resulted in a restriction to the hydrogen production when sulfate concentration was high. Domestic wastewaters contain low amounts of organic compounds and sulfate would be a better medium to enrich and maintain a hydrogen-producing biocathode dominated by SRB. Besides the risks of limited mass transport and precipitation caused by low potential, methane contamination in the hydrogen-rich environment was inevitable in the biocathode after long term operation due to methanogenic activities.

Bioanode as a limiting factor to biocathode performance in microbial electrolysis cells.

The bioanode is important for a microbial electrolysis cell (MEC) and its robustness to maintain its catalytic activity affects the performance of the whole system. Bioanodes enriched at a potential of +0.2V (vs. standard hydrogen electrode) were able to sustain their oxidation activity when the anode potential was varied from -0.3 up to +1.0V. Chronoamperometric test revealed that the bioanode produced peak current density of 0.36A/m2 and 0.37A/m2 at applied potential 0 and +0.6V, respectively. Meanwhile hydrogen production at the biocathode was proportional to the applied potential, in the range from -0.5 to -1.0V. The highest production rate was 7.4L H2/(m2 cathode area)/day at -1.0V cathode potential. A limited current output at the bioanode could halt the biocathode capability to generate hydrogen. Therefore maximum applied potential that can be applied to the biocathode was calculated as -0.84V without overloading the bioanode.

The biocathode of microbial electrochemical systems and microbially-influenced corrosion.

The cathode reaction is one of the most important limiting factors in bioelectrochemical systems even with precious metal catalysts. Since aerobic bacteria have a much higher affinity for oxygen than any known abiotic cathode catalysts, the performance of a microbial fuel cell can be improved through the use of electrochemically-active oxygen-reducing bacteria acting as the cathode catalyst. These consume electrons available from the electrode to reduce the electron acceptors present, probably conserving energy for growth. Anaerobic bacteria reduce protons to hydrogen in microbial electrolysis cells (MECs). These aerobic and anaerobic bacterial activities resemble those catalyzing microbially-influenced corrosion (MIC). Sulfate-reducing bacteria and homoacetogens have been identified in MEC biocathodes. For sustainable operation, microbes in a biocathode should conserve energy during such electron-consuming reactions probably by similar mechanisms as those occurring in MIC. A novel hypothesis is proposed here which explains how energy can be conserved by microbes in MEC biocathodes.