Recent Application of Nanomaterials to Overcome Technological Challenges of Microbial Electrolysis Cells.

Microbial electrolysis cells (MECs) have attracted significant interest as sustainable green hydrogen production devices because they utilize the environmentally friendly biocatalytic oxidation of organic wastes and electrochemical proton reduction with the support of relatively lower external power compared to that used by water electrolysis. However, the commercialization of MEC technology has stagnated owing to several critical technological challenges. Recently, many attempts have been made to utilize nanomaterials in MECs owing to the unique physicochemical properties of nanomaterials originating from their extremely small size (at least <100 nm in one dimension). The extraordinary properties of nanomaterials have provided great clues to overcome the technological hurdles in MECs. Nanomaterials are believed to play a crucial role in the commercialization of MECs. Thus, understanding the technological challenges of MECs, the characteristics of nanomaterials, and the employment of nanomaterials in MECs could be helpful in realizing commercial MEC technologies. Herein, the critical challenges that need to be addressed for MECs are highlighted, and then previous studies that used nanomaterials to overcome the technological difficulties of MECs are reviewed.

Scalability of microbial electrochemical technologies: Applications and challenges.

During wastewater treatment, microbial electrochemical technologies (METs) are a promising means for in situ energy harvesting and resource recovery. The primary constraint for such systems is scaling them up from the laboratory to practical applications. Currently, most research (∼90%) has been limited to benchtop models because of bioelectrochemical, economic, and engineering design limitations. Field trials, i.e., 1.5 m3 bioelectric toilet, 1000 L microbial electrolysis cell and industrial applications of METs have been conducted, and their results serve as positive indicators of their readiness for practical applications. Multiple startup companies have invested in the pilot-scale demonstrations of METs for industrial effluent treatment. Recently, advances in membrane/electrode modification, understanding of microbe-electrode interaction, and feasibility of electrochemical redox reactions have provided new directions for realizing the practical application. This study reviews the scaling-up challenges, success stories for onsite use, and readiness level of METs for commercialization that is inexpensive and sustainable.

Microbial community differences between propionate-fed microbial fuel cell systems under open and closed circuit conditions.

We report the electrochemical characterization and microbial community analysis of closed circuit microbial fuel cells (CC-MFCs) and open circuit (OC) cells continuously fed with propionate as substrate. Differences in power output between MFCs correlated with their polarization behavior, which is related to the maturation of the anodophilic communities. The microbial communities residing in the biofilm growing on the electrode, biofouled cation-exchange membrane and anodic chamber liquor of OC-and CC-MFCs were characterized by restriction fragment length polymorphism screening of 16S rRNA gene clone libraries. The results show that the CC-MFC anode was enriched in several microorganisms related to known electrochemically active and dissimilatory Fe(III) reducing bacteria, mostly from the Geobacter spp., to the detriment of Bacteroidetes abundant in the OC-MFC anode. The results also evidenced the lack of a specific pelagic community in the liquor sample. The biofilm growing on the cation-exchange membrane of the CC-MFC was found to be composed of a low-diversity community dominated by two microaerophilic species of the Achromobacter and Azovibrio genus.

Microbial fuel cell driven mineral rich wastewater treatment process for circular economy by creating virtuous cycles.

The aim of this work is to study for concurrent harvesting bioelectricity and struvite mineral from mineral rich wastewater containing with nitrogen (N) and phosphorous (P) contents using MFCs and a chemical precipitation system. Whole reaction was constructed to sequentially run hybrid reactor (consisting of MFCs and struvite precipitation), gravitational sedimentation, nitrogen purging and MFCs. The MFCs generated around 6.439 ± 0.481 mA and 2.084 ± 0.310 mW as Imax and Pmax, respectively under 2g/l of COD. More than 70% of C source, and around 95% of P and N sources have been removed. Struvite mineral was precipitated in the hybrid reactor after the injection of Mg2+ and collected in sedimentation tank. Economic feasibility and beneficial concerns were carefully investigated, and it is proposed for applications in the "decentralised treatment process" of agriculture and livestock wastewater in order to realise circular and strong economy in agriculture by creating virtuous cycles.

Electricity generation coupled to oxidation of propionate in a microbial fuel cell.

Propionate was used as fuel to enrich an electrochemically-active microbial consortium in a microbial fuel cell, and the bacterial consortium was analyzed by culture-independent methods including denaturing gradient gel electrophoresis (DGGE) of the 16S rDNA, and by fluorescent in situ hybridization (FISH). MFCs fed with propionate produced a current of 4.88 +/- 0.1 mA stably on 100 mg propionate/l as COD within 3 weeks of the enrichment. When the MFCs were fed with H2-saturated fuel containing propionate, the current dropped to 3.82 +/- 0.07 mA. The maximum current generated was up to 8.8 mA when MFCs were fed with 200 mg propionate/l as COD. The DGGE of 16S rDNA showed that propionate- enriched MFCs have a different bacterial population from that enriched with acetate and from the inoculum used for enrichment. The major member (42%) of the consortium was an unidentified bacterium followed by c, b, and d-proteobacteria.

Pressure Effects on the Magnetic Phase Diagram of the CeNMSb2 (NM: Au and Ag): A DFT Study.

We explore the influence of pressure on the magnetic ground state of the heavy-fermion antiferromagnet (ferromagnet) CeAuSb 2 (CeAgSb 2 ) using first-principles calculations. The total-energy differences obtained by including the spin-orbit interactions and the on-site Coulomb potential for the Ce-derived 4f-orbitals are necessary to realize the accurate magnetic ground state of CeNMSb 2 (NM: Au and Ag). According to our results, the appearance of a new magnetic phase of CeAuSb 2 (CeAgSb 2 ) at the pressure of 2.1 GPa (3.5 GPa) is due to the rotation of the magnetic easy axis from the <001> to the <100> direction. Additionally, our data confirm that CeAgSb 2 is antiferromagnetic (AFM) above a critical pressure P c , and such a tendency is expected for CeAuSb 2 and remains to be seen. Through the spin-orbit-coupling Hamiltonian and detailed information on the occupation of individual 4f-orbitals of the Ce atom obtained by the electronic-structure calculations, we can deduce the rotation of the magnetic easy axis upon the application of pressure. According to the present and previous studies, the differences among the magnetic properties of CeNMSb 2 (NM: Cu, Ag and Au) compounds are not due to the different noble metals, but due to the subtle differences in the relative position of Ce atoms and, in turn, different occupations of Ce 4f-orbitals.

Sulfonamide degradation and metabolite characterization in submerged membrane photobioreactors for livestock excreta treatment.

Residual veterinary antibiotics have been detected in livestock wastewater treatment plants. Despite the long retention time, antibiotic treatment efficiency has shown clear limitations. In this study, we evaluated submerged membrane photobioreactors (SMPBR) during sulfonamide antibiotic-containing livestock wastewater treatment under mixotrophic and photoautotrophic conditions. The results showed that microalgal sulfur degradation and consumption under mixotrophic conditions accelerated the biomass concentration increase to 2800 mg VSS/L compared to the 1800 mg VSS/L measured under photoautotrophic conditions. Although microalgal metabolites, such as soluble microbial products and extracellular polymeric substances, might cause membrane fouling in the SMPBR, we proved that microalgae could remove sulfonamide and release degradation-associated sulfur, along with nitrogen and phosphorus. Moreover, this study confirms the statistical correlation between metabolites and sulfonamides. In summary, the results of this study provide promising insights into antibiotic-containing livestock wastewater treatment.

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.

Optimal Temperature and Light Intensity for Improved Mixotrophic Metabolism of Chlorella sorokiniana Treating Livestock Wastewater.

Mixotrophic microalgal growth gives a great premise for wastewater treatment based on photoautotrophic nutrient utilization and heterotrophic organic removal while producing renewable biomass. There remains a need for a control strategy to enrich them in a photobioreactor. This study performed a series of batch experiments using a mixotroph, Chlorella sorokiniana, to characterize optimal guidelines of mixotrophic growth based on a statistical design of the experiment. Using a central composite design, this study evaluated how temperature and light irradiance are associated with CO2 capture and organic carbon respiration through biomass production and ammonia removal kinetics. By conducting regressions on the experimental data, response surfaces were created to suggest proper ranges of temperature and light irradiance that mixotrophs can beneficially use as two types of energy sources. The results identified that efficient mixotrophic metabolism of Chlorella sorokiniana for organics and inorganics occurs at the temperature of 30-40°C and diurnal light condition of 150-200 µmol E·m2·s-1. The optimal specific growth rate and ammonia removal rate were recorded as 0.51/d and 0.56/h on average, respectively, and the confirmation test verified that the organic removal rate was 105 mg COD·l-1·d-1. These results support the development of a viable option for sustainable treatment and effluent quality management of problematic livestock wastewater.

Self-recoverable voltage reversal in stacked microbial fuel cells due to biofilm capacitance.

In order to assess the effects of biofilm capacitance on self-recovering voltage reversals, the restored current is determined and compared with the measured biofilm capacitance by analyzing the results of electrochemical impedance spectroscopy. This comparison demonstrates that self-recovering voltage reversals are caused by temporary damage to, and the recovery of, biofilm capacitance which arises due to the ability of redox enzymes in the electron transfer system to temporarily store electrons. Thus, the development of procedures for voltage reversal control and for the maintenance of serially connected microbial fuel cells (MFCs) should take into account such temporary voltage reversal phenomenon. This discovery and characterization of self-recovering voltage reversals is expected to be practically useful to enhance the reliability of MFCs to be scaled up and implemented in practical systems.

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.

Improved Electricity Generation by a Microbial Fuel Cell after Pretreatment of Ammonium and Nitrate in Livestock Wastewater with Microbubbles and a Catalyst.

Livestock wastewater containing high concentrations of ammonium and nitrate ions was pretreated with microbubbles and an Fe/MgO catalyst prior to its application in microbial fuel cells because high ion concentrations can interfere with current generation. Therefore, tests were designed to ascertain the effect of pretreatment on current generation. In initial tests, the optimal amount of catalyst was found to be 300 g/l. When 1,000 ml/min O2 was used as the oxidant, the removal of ammonium- and nitrate-nitrogen was highest. After the operating parameters were optimized, the removal of ammonium and nitrate ions was quantified. The maximum ammonium removal was 32.8%, and nitrate was removed by up to 75.8% at a 500 g/l catalyst concentration over the course of the 2 h reaction time. The current was about 0.5 mA when livestock wastewater was used without pretreatment, whereas the current increased to 2.14 ± 0.08 mA when livestock wastewater was pretreated with the method described above. This finding demonstrates that a 4-fold increase in the current can be achieved when using pretreated livestock wastewater. The maximum power density and current density performance were 10.3 W/m³ and 67.5 A/m³, respectively, during the evaluation of the microbial fuel cells driven by pretreated livestock wastewater.

Characterization of Polyester Cloth as an Alternative Separator to Nafion Membrane in Microbial Fuel Cells for Bioelectricity Generation Using Swine Wastewater.

Polyester cloth (PC) was selected as a prospective inexpensive substitute separator material for microbial fuel cells (MFCs). PC was compared with a traditional Nafion proton exchange membrane (PEM) as an MFC separator by analyzing its physical and electrochemical properties. A single layer of PC showed higher mass transfer (e.g., for O2/H⁺/ions) than the Nafion PEM; in the case of oxygen mass transfer coefficient (ko), a rate of 50.0 × 10⁻5 cm·s⁻¹ was observed compared with a rate of 20.8 × 10⁻5 cm/s in the Nafion PEM. Increased numbers of PC layers were found to reduce the oxygen mass transfer coefficient. In addition, the diffusion coefficient of oxygen (DO) for PC (2.0-3.3 × 10⁻6 cm²/s) was lower than that of the Nafion PEM (3.8 × 10⁻6 cm²/s). The PC was found to have a low ohmic resistance (0.29-0.38 Ω) in the MFC, which was similar to that of Nafion PEM (0.31 Ω); this resulted in comparable maximum power density and maximum current density in MFCs with PC and those with Nafion PEMs. Moreover, a higher average current generation was observed in MFCs with PC (104.3 ± 15.3 A/m³) compared with MFCs with Nafion PEM (100.4 ± 17.7 A/m³), as well as showing insignificant degradation of the PC surface, during 177 days of use in swine wastewater. These results suggest that PC separators could serve as a low-cost alternative to Nafion PEMs for construction of cost-effective MFCs.

ARD1-mediated Hsp70 acetylation balances stress-induced protein refolding and degradation.

Heat shock protein (Hsp)70 is a molecular chaperone that maintains protein homoeostasis during cellular stress through two opposing mechanisms: protein refolding and degradation. However, the mechanisms by which Hsp70 balances these opposing functions under stress conditions remain unknown. Here, we demonstrate that Hsp70 preferentially facilitates protein refolding after stress, gradually switching to protein degradation via a mechanism dependent on ARD1-mediated Hsp70 acetylation. During the early stress response, Hsp70 is immediately acetylated by ARD1 at K77, and the acetylated Hsp70 binds to the co-chaperone Hop to allow protein refolding. Thereafter, Hsp70 is deacetylated and binds to the ubiquitin ligase protein CHIP to complete protein degradation during later stages. This switch is required for the maintenance of protein homoeostasis and ultimately rescues cells from stress-induced cell death in vitro and in vivo. Therefore, ARD1-mediated Hsp70 acetylation is a regulatory mechanism that temporally balances protein refolding/degradation in response to stress.

Improvement of a microbial fuel cell performance as a BOD sensor using respiratory inhibitors.

Studies were made to improve the performance of a microbial fuel cell (MFC) as a biochemical oxygen demand (BOD) sensor. The signal from MFCs decreased in the presence of electron acceptors of higher redox potential such as nitrate and oxygen. The addition of azide and cyanide did not change the signal in the absence of the electron acceptors. The respiratory inhibitors eliminated the inhibitory effects of the electron acceptors on the current generation from MFCs. Similar results were obtained using oligotrophic MFCs fed with an environmental sample that contained nitrate. The use of the respiratory inhibitors is therefore recommended for the accurate BOD measurement of environmental samples containing nitrate and/or oxygen with an MFC-type BOD sensor.

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.

Autoacetylation regulates differentially the roles of ARD1 variants in tumorigenesis.

ARD1 is an acetyltransferase with several variants derived from alternative splicing. Among ARD1 variants, mouse ARD1(225) (mARD1(225)), mouse ARD1(235) (mARD1(235)), and human ARD1(235) (hARD1(235)) have been the most extensively characterized and are known to have different biological functions. In the present study, we demonstrated that mARD1(225), mARD1(235), and hARD1(235) have conserved autoacetylation activities, and that they selectively regulate distinct roles of ARD1 variants in tumorigenesis. Using purified recombinants for ARD1 variants, we found that mARD1(225), mARD1(235), and hARD1(235) undergo similar autoacetylation with the target site conserved at the Lys136 residue. Moreover, functional investigations revealed that the role of mARD1(225) autoacetylation is completely distinguishable from that of mARD1(235) and hARD1(235). Under hypoxic conditions, mARD1(225) autoacetylation inhibited tumor angiogenesis by decreasing the stability of hypoxia-inducible factor-1α (HIF-1α). Autoacetylation stimulated the catalytic activity of mARD1(225) to acetylate Lys532 of the oxygen-dependent degradation (ODD) domain of HIF-1α, leading to the proteosomal degradation of HIF-1α. In contrast, autoacetylation of mARD1(235) and hARD1(235) contributed to cellular growth under normoxic conditions by increasing the expression of cyclin D1. Taken together, these data suggest that autoacetylation of ARD1 variants differentially regulates angiogenesis and cell proliferation in an isoform-specific manner.

Operational parameters affecting the performannce of a mediator-less microbial fuel cell.

A mediator-less microbial fuel cell was optimized in terms of various operating conditions. Current generation was dependent on several factors such as pH, resistance, electrolyte used, and dissolved oxygen concentration in the cathode compartment. The highest current was generated at pH 7. Under the operating conditions, the resistance was the rate-determining factor at over 500 omega. With resistance lower than 500 omega, proton transfer and dissolved oxygen (DO) supply limited the cathode reaction. A high strength buffer reduced the proton limitation to some extent. The DO concentration was around 6 mg l(-1) at the DO limited condition. The fact that oxygen limitation was observed at high DO concentration is believed to be due to the poor oxygen reducing activity of the electrode used, graphite. The current showed linear relationship with the fuel added at low concentration, and the electronic charge was well correlated with substrate concentration from up to 400 mg l(-1) of COD(cr). The microbial fuel cell might be used as a biochemical oxygen demand (BOD) sensor.

Continuous determination of biochemical oxygen demand using microbial fuel cell type biosensor.

A mediator-less microbial fuel cell (MFC) was used as a biochemical oxygen demand (BOD) sensor in an amperometric mode for real-time wastewater monitoring. At a hydraulic retention time of 1.05 h, BOD values of up to 100 mg/l were measured based on a linear relationship, while higher BOD values were measured using a lower feeding rate. About 60 min was required to reach a new steady-state current after the MFCs had been fed with different strength artificial wastewaters (Aws). The current generated from the MFCs fed with AW with a BOD of 100 mg/l was compared to determine the repeatability, and the difference was less than 10%. When the MFC was starved, the original current value was regained with a varying recovery time depending on the length of the starvation. During starvation, the MFC generated a background level current, probably due to an endogenous metabolism.

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.