Determination of optimum electrical connection mode for multi-electrode-embedded microbial fuel cells coupled with anaerobic digester for enhancement of swine wastewater treatment efficiency and energy recovery.

In this work, three multi-electrode-embedded microbial fuel cells (MFCs) were connected sequentially and operated in series and parallel modes, fed by effluent of an anaerobic digester continuously operated using swine wastewater. The anaerobic digester achieved ~0.75 CH4 L d-1 while removing 71.2% of COD and 0.8% of ammonia, which was comparable to the literatures reported. The MFCs removed additional COD from the anaerobic digester effluent, achieving the lowest concentration in the last unit, leading to a voltage reversal in the serially-connected unit. The MFCs connected and operated in parallel mode showed the highest power density of ~25 W m-3, which is 18% higher compared to the one operated in series mode. These results definitively show that differences in substrate concentrations among MFC units are inevitable with sequential flow. Further, a parallel connection mode of operation is necessary to achieve stable, long-term power generation from MFC units, without any electrical malfunction.

Induction of cathodic voltage reversal and hydrogen peroxide synthesis in a serially stacked microbial fuel cell.

We developed an innovative strategy to address the inhibition of anode-respiring bacteria due to voltage reversal in serially stacked microbial fuel cells by inducing cathodic voltage reversal and H2O2 production. When platinum-coated carbon (Pt/C) cathodes were employed (stacked MFCPt/C) and the MFC was operated with acetate medium, the last unit (MFC 4) caused a voltage reversal of -0.8 V with a substantial anode overpotential of 1.22 V. After replacing the Pt/C cathode with a Pt-free carbon gas diffusion electrode in MFC 4, an electrode overpotential, approximately 0.5 V, was shifted from the anode to the cathode, inducing cathodic voltage reversal. Under cathodic voltage reversal, MFC 4 generated H2O2 at a production rate of 117 mg H2O2/m2-h. Hence, under cathodic voltage reversal induced by Pt-free cathodes, due to less anode polarization, the anode-respiring activity can largely be sustained in a stacked MFC that treats organic wastewater consistently and the quality of treated wastewater may be improved with energy-efficient and on-site generated H2O2.

Hydrogen peroxide production in a pilot-scale microbial electrolysis cell.

A pilot-scale dual-chamber microbial electrolysis cell (MEC) equipped with a carbon gas-diffusion cathode was evaluated for H2O2 production using acetate medium as the electron donor. To assess the effect of cathodic pH on H2O2 yield, the MEC was tested with an anion exchange membrane (AEM) and a cation exchange membrane (CEM), respectively. The maximum current density reached 0.94-0.96 A/m2 in the MEC at applied voltage of 0.35-1.9 V, regardless of membranes. The highest H2O2 conversion efficiency was only 7.2 ± 0.09% for the CEM-MEC. This low conversion would be due to further H2O2 reduction to H2O on the cathode or H2O2 decomposition in bulk liquid. This low H2O2 conversion indicates that large-scale MECs are not ideal for production of concentrated H2O2 but could be useful for a sustainable in-situ oxidation process in wastewater treatment.

Elimination of Power Overshoot at Bioanode through Assistance Current in Microbial Fuel Cells.

The power overshoot generated by electron depletion in microbial fuel cells (MFCs) was characterized in this study. Various causes of power overshoot, identified in previous studies, are discussed in terms of their plausible contributions to electron depletion. We found that power overshoot occurred if the anodic overpotential generated by electron depletion exceeded the cathodic overpotential. The introduction of assistance current from anode connections, which ameliorated the electron depletion in the MFCs, immediately eliminated the power overshoot. As a result, if the electron production at the anode exceeded electron reduction at the cathode, a power overshoot was not generated. The results revealed that introducing assistance current supplied from an additional anode to the limited anode eliminated power overshoot. The power overshoot is not generated by kinetic limitation at the cathode; it is only generated by the kinetic limitation at the anode. The mechanism underlying power overshoot should be considered in the design of MFCs to improve reliability, particularly in scaled-up plant applications. The proposed technique is more practical than previously proposed methods.

The Roles of Biofilm Conductivity and Donor Substrate Kinetics in a Mixed-Culture Biofilm Anode.

We experimentally assessed the kinetics and thermodynamics of electron transfer (ET) from the donor substrate (acetate) to the anode for a mixed-culture biofilm anode. We interpreted the results with a modified biofilm-conduction model consisting of three ET steps in series: (1) intracellular ET, (2) non-Ohmic extracellular ET (EET) from an outer membrane protein to an extracellular cofactor (EC), and (3) ET from the EC to the anode by Ohmic-conduction in the biofilm matrix. The steady-state current density was 0.82 ± 0.03 A/m2 in a miniature microbial electrochemical cell operated at fixed anode potential of -0.15 V versus the standard hydrogen electrode. Illumina 16S-rDNA and -rRNA sequences showed that the Geobacter genus was less than 30% of the community of the biofilm anode. Biofilm conductivity was high at 2.44 ± 0.42 mS/cm, indicating that the maximum current density could be as high as 270 A/m2 if only Ohmic-conduction EET was limiting. Due to the high biofilm conductivity, the maximum energy loss for Ohmic-conduction EET was negligible, 0.085 mV. The energy loss in the second ET step also was small, only 20 mV, and the potential for the EC involved in the second ET was -0.15 V, a value documenting that >99% of the EC was in the oxidized state. Monod kinetics for utilization of acetate were relatively slow, and at least 87% of the energy loss was in the intracellular step. Thus, intracellular ET was the main kinetic and thermodynamic bottleneck to ET from donor substrate to the anode for a highly conductive biofilm.

pH-dependent ammonia removal pathways in microbial fuel cell system.

In this work, ammonia removal paths in microbial fuel cells (MFCs) under different initial pH conditions (pH 7.0, 8.0, and 8.6) were investigated. At a neutral pH condition (pH 7.0), MFC used an electrical energy of 27.4% and removed 23.3% of total ammonia by electrochemical pathway for 192h. At the identical pH condition, 36.1% of the total ammonia was also removed by the biological path suspected to be biological ammonia oxidation process (e.g., Anammox). With the initial pH increased, the electrochemical removal efficiency decreased to less than 5.0%, while the biological removal efficiency highly increased to 61.8%. In this study, a neutral pH should be maintained in the anode to utilize MFCs for ammonia recovery via electrochemical pathways from wastewater stream.

Development of anode zone using dual-anode system to reduce organic matter crossover in membraneless microbial fuel cells.

To prevent the occurrence of the organic crossover in membraneless microbial fuel cells (ML-MFCs), dual-anode MFC (DA-MFC) was designed from multi-anode concept to ensure anode zone. The anode zone addressed increase the utilization of organic matter in ML-MFCs, as the result, the organic crossover was prevented and performance of MFCs were enhanced. The maximum power of the DA-MFC was 0.46mW, which is about 1.56 times higher than the ML-MFC (0.29mW). Furthermore, the DA-MFC had advantage in correlation of organic substance concentration and dissolved oxygen concentration, and even electric over-potential. In addition, in terms of cathode fouling, the DA-MFC showed clearer surface. Hence, the anode zone should be considered in the advanced ML-MFC for practically use in wastewater treatment process, and also for scale-up of MFCs.

Understanding energy loss in parallelly connected microbial fuel cells: Non-Faradaic current.

In this work, the mechanisms of energy loss in parallel connection of microbial fuel cells (MFCs) is explored using two MFC units producing different open circuit voltage (OCV) and current. In open circuit mode, non-Faradaic current flows in low OCV unit, implying energy loss caused by different OCVs in parallelly stacked MFCs. In a stacked MFC in parallel under close circuit mode, it is confirmed that energy loss occurs until the working voltage in high OCV unit becomes identical to the other unit having low OCV. This result indicates that different voltage between individual MFC units can cause energy loss due to both non-Faradic and Faradaic current that flow from high voltage unit to low voltage unit even in parallelly stacked MFCs.

Increased Power in Sediment Microbial Fuel Cell: Facilitated Mass Transfer via a Water-Layer Anode Embedded in Sediment.

We report a methodology for enhancing the mass transfer at the anode electrode of sediment microbial fuel cells (SMFCs), by employing a fabric baffle to create a separate water-layer for installing the anode electrode in sediment. The maximum power in an SMFC with the anode installed in the separate water-layer (SMFC-wFB) was improved by factor of 6.6 compared to an SMFC having the anode embedded in the sediment (SMFC-woFB). The maximum current density in the SMFC-wFB was also 3.9 times higher (220.46 mA/m2) than for the SMFC-woFB. We found that the increased performance in the SMFC-wFB was due to the improved mass transfer rate of organic matter obtained by employing the water-layer during anode installation in the sediment layer. Acetate injection tests revealed that the SMFC-wFB could be applied to natural water bodies in which there is frequent organic contamination, based on the acetate flux from the cathode to the anode.

Contribution of Liquid/Gas Mass-Transfer Limitations to Dissolved Methane Oversaturation in Anaerobic Treatment of Dilute Wastewater.

The mechanisms controlling the accumulation of dissolved methane in anaerobic membrane bioreactors (AnMBRs) treating a synthetic dilute wastewater (a glucose medium) were assessed experimentally and theoretically. The AnMBR was maintained at a temperature of 24-26 °C as the organic loading rate increased from 0.39 to 1.1 kg COD/m(3)-d. The measured concentration of dissolved methane was consistently 2.2- to 2.5-fold larger than the concentration of dissolved methane at thermodynamic equilibrium with the measured CH4 partial pressure, and the fraction of dissolved methane was as high as 76% of the total methane produced. The low gas production rate in the AnMBR significantly slowed the mass transport of dissolved methane to the gas phase. Although the production rate of total methane increased linearly with the COD loading rate, the concentration of dissolved methane only slightly increased with an increasing organic loading rate, because the mass-transfer rate increased by almost 5-fold as the COD loading increased from 0.39 to 1.1 kg COD/m(3)-d. Thus, slow mass transport kinetics exacerbated the situation in which dissolved methane accounted for a substantial fraction of the total methane generated from the AnMBR.

Bioelectronic platforms for optimal bio-anode of bio-electrochemical systems: From nano- to macro scopes.

The current trend of bio-electrochemical systems is to improve strategies related to their applicability and potential for scaling-up. To date, literature has suggested strategies, but the proposal of correlations between each research field remains insufficient. This review paper provides a correlation based on platform techniques, referred to as bio-electronics platforms (BEPs). These BEPs consist of three platforms divided by scope scale: nano-, micro-, and macro-BEPs. In the nano-BEP, several types of electron transfer mechanisms used by electrochemically active bacteria are discussed. In the micro-BEP, factors affecting the formation of conductive biofilms and transport of electrons in the conductive biofilm are investigated. In the macro-BEP, electrodes and separators in bio-anode are debated in terms of real applications, and a scale-up strategy is discussed. Overall, the challenges of each BEP are highlighted, and potential solutions are suggested. In addition, future research directions are provided and research ideas proposed to develop research interest.

Coupling of anaerobic digester and microbial fuel cell for COD removal and ammonia recovery.

Microbial fuel cells (MFCs) were investigated for use in removing total ammonia nitrogen (TAN) and residual COD from effluent digested in an anaerobic digester (AD) fed with actual swine wastewater for 32 days in batch mode. Cumulative COD removal in the AD was as high as 59,647±2096 mg/L (80.5% removed), whereas TAN removal in the AD was negligible at 296±116 mg-N/L (5.8% removed), causing a decrease in the COD/TAN ratio from 14.5 to 3.0. In a subsequent MFC system, 77.5% of TAN was removed at 36 days, leading to an increase in COD/TAN ratio from 4.6 to 8.1. As a result, the COD in the anode was further reduced from 19,319±417 mg/L to 7519±554 mg/L (61.1% removed). From these results, removing the TAN in MFCs was found to increase the COD/TAN ratio, with the COD being further degraded.

Characterization and optimization of cathodic conditions for H2O2 synthesis in microbial electrochemical cells.

Cathode potential and O2 supply methods were investigated to improve H2O2 synthesis in an electrochemical cell, and optimal cathode conditions were applied for microbial electrochemical cells (MECs). Using aqueous O2 for the cathode significantly improved current density, but H2O2 conversion efficiency was negligible at 0.3-12%. Current density decreased for passive O2 diffusion to the cathode, but H2O2 conversion efficiency increased by 65%. An MEC equipped with a gas diffusion cathode was operated with acetate medium and domestic wastewater, which presented relatively high H2O2 conversion efficiency from 36% to 47%, although cathode overpotential was fluctuated. Due to different current densities, the maximum H2O2 production rate was 141 mg H2O2/L-h in the MEC fed with acetate medium, but it became low at 6 mg H2O2/L-h in the MEC fed with the wastewater. Our study clearly indicates that improving anodic current density and mitigating membrane fouling would be key parameters for large-scale H2O2-MECs.

Performance variation according to anode-embedded orientation in a sediment microbial fuel cell employing a chessboard-like hundred-piece anode.

The effect of two different anode-embedding orientations, lengthwise- and widthwise-embedded anodes was explored, on the performance of sediment microbial fuel cells (SMFCs) using a chessboard anode. The maximum current densities and power densities in SMFCs having lengthwise-embedded anodes (SLA1-SLA10) varied from 38.2mA/m(2) to 121mA/m(2) and from 5.5mW/m(2) to 20mW/m(2). In comparison, the maximum current densities and maximum power densities in SMFCs having anodes widthwise-embedded between 0cm to 8cm (SWA2-SWA5) increased from 82mA/m(2) to 140mA/m(2) and from 14.7mW/m(2) to 31.1mW/m(2) as the anode depth became deeper. Although there was a difference in the performance among SWA5-SWA10, it was considered negligible. Hence, it is concluded that it is important to embed anodes widthwise at the specific anode depths, in order to improve of SMFC performance. Chessboard anode used in this work could be a good option for the determination of optimal anode depths.

New architecture for modulization of membraneless and single-chambered microbial fuel cell using a bipolar plate-electrode assembly (BEA).

A new architecture for a membraneless and single-chambered microbial fuel cell (MFC) which has a unique bipolar plate-electrode assembly (BEA) design was demonstrated. The maximum power of MFC units connected in series (denoted as a stacked MFC) was up to 22.8±0.13 mW/m(2) for 0.946±0.003 V working voltage, which is 2.5 times higher than the averaged maximum power density of the non-stacked MFC units. The power density in the stacked MFC using BEA was comparable to the stacked MFC using electric wire. These results demonstrate that BEAs having air-exposed cathodes can potentially be used in the stacking of membraneless single-chambered MFCs. In addition, we confirmed that the current in the stacked mode flowed faster than the non-stacked mode due to voltage increase by series connection, and the poorest of the stacked units quickly faced current depletion at higher external resistance than the non-stacked mode, leading to voltage reversal. These results imply that stacked MFC units require a relatively large current capacity in order to prevent high voltage reversal at high current region. To increase total current capacity and prevent voltage reversal of stacked MFC units, we suggested series/parallel-integrated MFC module system for scaling-up. This new concept could likely allow the application of MFC technology to be extended to various wastewater treatment processes or plants.

Occurrence and implications of voltage reversal in stacked microbial fuel cells.

Voltage reversal in stacked microbial fuel cells (MFCs) is a significant challenge that must be addressed, and the information on its definite cause and occurrence process is still obscure. In this work, we first demonstrated that different anodic reaction rates caused voltage reversal in a stacked MFC. Sluggish reaction rates on the anode in unit 1 of the stacked MFC resulted in a significantly increased anode overpotential of up to 0.132 V, as compared to negligible anode overpotential (0.0247 V) in unit 2. This work clearly verified the process of voltage reversal in the stacked MFC. As the current was gradually increased in the stacked MFC, the voltage in the stacked unit 1 decreased to 0 V prior to that of the stacked unit 2. Then, when the voltage in unit 1 became 0 V, it was converted from a galvanic cell to an electrochemical cell powered by unit 2. We found that the stacked unit 2 provided electrical energy for the stacked unit 1 as a power supply. Finally, the anode potential of the stacked unit 1 significantly increased over cathode potential as current increased further, which caused voltage reversal in unit 1. Voltage reversal occurs in stacked MFCs as a result of non-spontaneous anode overpotential in a unit MFC that has sluggish anode kinetics compared to the other unit MFCs.

Microbial fuel cells as discontinuous portable power sources: syntropic interactions with anode-respiring bacteria.

For microbial fuel cells (MFCs) to work as portable power sources used in a discontinuous manner, anode-respiring bacteria (ARB) should survive for at least several days in the absence of exogenous electron donors, and immediately generate current upon addition of an electron donor. Here, we proved that biopolymer-accumulating bacteria provide substrate (fuel) for ARB to generate current in lack of exogenous electron donor in 4 days, which allows MFCs to be used as portable power sources.

Power density enhancement of anion-exchange membrane-installed microbial fuel cell under bicarbonate-buffered cathode condition.

We introduce a high-performance microbial fuel cell (MFC) that was operated using a 0.1 M bicarbonate buffer as the cathodic electrolyte. The MFC had a 136.42 mW/m(2) maximum power density under continuous feeding of 5 mM acetate as fuel. Results of the electrode potential measurements showed that the cathode potential of the bicarbonate-buffered condition was higher than the phosphate-buffered condition, although the phosphate condition had less interfacial resistance between the membrane and electrolyte. Therefore, we posit here that the increased power of the bicarbonate-buffered MFC may be caused by the higher cathode potential rather than by the interfacial membrane-electrolyte resistance.

Comparison in performance of sediment microbial fuel cells according to depth of embedded anode.

Five rigid graphite plates were embedded in evenly divided sections of sediment, ranging from 2 cm (A1) to 10 cm (A5) below the top sediment layer. The maximum power and current of the MFCs increased in depth order; however, despite the increase in the internal resistance, the power and current density of the A5 MFC were 2.2 and 3.5 times higher, respectively, than those of the A1 MFC. In addition, the anode open circuit potentials (OCPs) of the sediment microbial fuel cells (SMFCs) became more negative with sediment depth. Based on these results, it could be then concluded that as the anode-embedding depth increases, that the anode environment is thermodynamically and kinetically favorable to anodophiles or electrophiles. Therefore, the anode-embedding depth should be considered an important parameter that determines the performance of SMFCs, and we posit that the anode potential could be one indicator for selecting the anode-embedding depth.

Scaling-up microbial fuel cells: configuration and potential drop phenomenon at series connection of unit cells in shared anolyte.

To scale-up microbial fuel cells (MFCs), installing multiple unit cells in a common reactor has been proposed; however, there has been a serious potential drop when connecting unit cells in series. To determine the source of the loss, a basic stack-MFC (BS-MFC) has been devised, and the results show that the phenomenon is due to ions on the anode electrode traveling through the electrolyte to be reduced at the cathode connected in series. As calculated by means of the percentage potential drop, the degree of potential drop decreased with an increase in the unit-cell distance. When the distance was increased from 1 to 8 cm, the percentage potential drop in BS-MFC1 decreased from 46.76 ± 0.90 to 45.08 ± 0.70 % and in BS-MFC2 from 46.41 ± 0.95 to 43.82 ± 2.23 %. As the p-value of the t-test was lower than 0.05, the difference was considered significant; however, if the unit cells are installed far enough from each other to avoid the potential drop phenomenon, the system will be less dense, consequently reducing the ratio of electrode area per volume of anode compartment and decreasing the power density of the system. Finally, this study suggests design criteria for scaling-up MFC systems: Multiple-electrode-installed MFCs are modularized, and the unit cells are connected in series across the module (connecting each unit cell does not share the anolyte).