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Wastewater treatment plants have two persistent financial and energetic drains, the carbon dioxide content of biogas, which limits its commercial sale, and the presence of trace organics in the wastewater effluent, which damages the aquatic ecosystem, like the Great Barrier Reef. Biogas is a renewable methane resource that is underutilized due to the variable CO2 content (~40%). Biogas is energy intensive to purify and limited by the economy of scale (> 8.85 GJ/h) to large‐scale purification methods, thus small‐scale processes require development. Electrocatalytic microbes native to wastewater have been shown to convert CO2 to CH4 and acetate, however complete conversion of the CO2 content to CH4 is energy intensive. Here we show a low power bioelectrochemical fuel cell design to purify biogas to pipeline quality methane (98%), manufacture methane and/or acetate, and remove trace organics, using HCO3− as the transport charge carrier from dissolved CO2 from the biogas through an anion exchange membrane. This decreased the power required to separate CO2 from methane in biogas on a molar basis, resulting in a net energy recovery similar to current industrial systems. Magnesium anode use resulted in an energy positive system. Tests evaluated the influence of cathode potential on the current density, HCO3− ion flux and the rates and efficiencies of methane production, resulting in optimization at −0.7 V versus standard hydrogen electrode (SHE). A techno‐economic analysis modeled a positive return on investment for scaled‐up production to purify small biogas streams that are otherwise financially unrecoverable. Carbon sequestration by production of methane, acetate and solid fertilizers demonstrated profitable and energy efficient waste‐to‐resource conversion. Methane is manufactured from carbon dioxide simultaneous to biogas purification for carbon neutral energy production in a biological fuel cell during the final process step of wastewater treatment. Lab tests demonstrate proof of concept during wastewater treatment. The techno‐economic analysis (financial and manufacturing model) demonstrates industrial scale operation can make a profit at manufacturing renewable methane and/or acetate. [ABSTRACT FROM AUTHOR]

Industrial applications of microbial electrochemical systems will require regular maintenance shutdowns, involving inspections and component replacements to extend the lifespan of the system. Here, we examined the impact of such shutdowns on the performance of three electrode materials (i. e., platinized titanium, graphite, and nickel) as cathodes in a microbial electrochemical system that would be used for electromethanogenesis in power‐to‐gas applications. We focused on methane (CH4) production from hydrogen (H2) and carbon dioxide (CO2) using Methanothermobacter thermautotrophicus. We showed that the platinized titanium cathode resulted in high volumetric CH4 production rates and Coulombic efficiencies. Using a graphite cathode would be more cost‐effective than using the platinized titanium cathode in microbial electrochemical systems, but showed an inferior performance. The microbial electrochemical system with the nickel cathode showed improvements compared to the graphite cathode. Additionally, this system with a nickel cathode demonstrated the fastest recovery during a shutdown experiment compared to the other two cathodes. Fluctuations in pH and nickel concentrations in the catholyte during power interruptions affected CH4 production recovery in the system with the nickel cathode. This research enhances understanding of the integration of biological and electrochemical processes in microbial electrochemical systems, providing insights into electrode selection and operating strategies for effective and sustainable CH4 production. [ABSTRACT FROM AUTHOR]

Abstract Industrial applications of microbial electrochemical systems will require regular maintenance shutdowns, involving inspections and component replacements to extend the lifespan of the system. Here, we examined the impact of such shutdowns on the performance of three electrode materials (i. e., platinized titanium, graphite, and nickel) as cathodes in a microbial electrochemical system that would be used for electromethanogenesis in power‐to‐gas applications. We focused on methane (CH4) production from hydrogen (H2) and carbon dioxide (CO2) using Methanothermobacter thermautotrophicus. We showed that the platinized titanium cathode resulted in high volumetric CH4 production rates and Coulombic efficiencies. Using a graphite cathode would be more cost‐effective than using the platinized titanium cathode in microbial electrochemical systems, but showed an inferior performance. The microbial electrochemical system with the nickel cathode showed improvements compared to the graphite cathode. Additionally, this system with a nickel cathode demonstrated the fastest recovery during a shutdown experiment compared to the other two cathodes. Fluctuations in pH and nickel concentrations in the catholyte during power interruptions affected CH4 production recovery in the system with the nickel cathode. This research enhances understanding of the integration of biological and electrochemical processes in microbial electrochemical systems, providing insights into electrode selection and operating strategies for effective and sustainable CH4 production.

Biogas has long been used as a household cooking fuel in many tropical counties, and it has the potential to be a significant energy source beyond household cooking fuel. In this study, we describe the use of low electrical energy input in an anaerobic digestion process using a microbial electrochemical cell (MEC) to promote methane content in biogas at 18, 28, and 37 °C. Although the maximum amount of biogas production was at 37 °C (25 cm3), biogas could be effectively produced at lower temperatures, i.e., 18 (13 cm3) and 28 °C (19 cm3), with an external 2 V power input. The biogas production of 13 cm3 obtained at 18 °C was ~65-fold higher than the biogas produced without an external power supply (0.2 cm3). This was further enhanced by 23% using carbon-nanotubes-treated (CNT) graphite electrodes. This suggests that the MEC can be operated at as low as 18 °C and still produce significant amounts of biogas. The share of CH4 in biogas produced in the controls was 30%, whereas the biogas produced in an MEC had 80% CH4. The MEC effectively reduced COD to 42%, whereas it consumed 98% of reducing sugars. Accordingly, it is a suitable method for waste/manure treatment. Molecular characterization using 16s rRNA sequencing confirmed the presence of methanogenic bacteria, viz., Serratia liquefaciens and Zoballella taiwanensis, in the inoculum used for the fermentation. Consistent with recent studies, we believe that electromethanogenesis will play a significant role in the production of value-added products and improve the management of waste by converting it to energy.

Biogas has long been used as a household cooking fuel in many tropical counties, and it has the potential to be a significant energy source beyond household cooking fuel. In this study, we describe the use of low electrical energy input in an anaerobic digestion process using a microbial electrochemical cell (MEC) to promote methane content in biogas at 18, 28, and 37 °C. Although the maximum amount of biogas production was at 37 °C (25 cm3), biogas could be effectively produced at lower temperatures, i.e., 18 (13 cm3) and 28 °C (19 cm3), with an external 2 V power input. The biogas production of 13 cm3 obtained at 18 °C was ~65-fold higher than the biogas produced without an external power supply (0.2 cm3). This was further enhanced by 23% using carbon-nanotubes-treated (CNT) graphite electrodes. This suggests that the MEC can be operated at as low as 18 °C and still produce significant amounts of biogas. The share of CH4 in biogas produced in the controls was 30%, whereas the biogas produced in an MEC had 80% CH4. The MEC effectively reduced COD to 42%, whereas it consumed 98% of reducing sugars. Accordingly, it is a suitable method for waste/manure treatment. Molecular characterization using 16s rRNA sequencing confirmed the presence of methanogenic bacteria, viz., Serratia liquefaciens and Zoballella taiwanensis, in the inoculum used for the fermentation. Consistent with recent studies, we believe that electromethanogenesis will play a significant role in the production of value-added products and improve the management of waste by converting it to energy. [ABSTRACT FROM AUTHOR]

Electromethanogenesis is a process of microbial electrosynthesis (MES) in which electroactive microorganisms reduce carbon dioxide (CO2) to produce methane (CH4), using a cathode as an electron donor. The efficiency of this reaction is greatly determined by the establishment of a robust microbial community on the biocathodes, which eventually affects the global performance of the bioreactor. Moreover, the development of the biofilm depends on several characteristics of the electrodes, more specifically their material and geometry. Since electrode geometry is a crucial parameter, this study aims at evaluating the sole influence of the electrode shape by installing carbon‐based electrodes with two different constructions (brush and carbon felt) of biocathodes in an electromethanogenic reactor for CO2 capture. The overall performance of the reactors showed coulombic efficiencies around 100%, with high‐quality biogas reaching methane concentrations above 90%. The results reveal that the electrode geometry affects the individual biocathode performance, and the carbon brush showed a bigger contribution to current generation and electrical capacitance, exhibiting higher peak hydrogen production compared to the carbon felt, which could be reflected in higher CO2 capture and methane generation. Both geometries showed a greater proliferation of archaea over bacteria (between 53 and 85%), which was more significant on the brush than on the carbon felt. Archaea community was dominated by Methanobacterium in carbon felt electrodes and codominated with Methanobrevibacter in brush electrodes, while bacteria analyses showed a very similar community for both geometries. © 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd. [ABSTRACT FROM AUTHOR]

[Display omitted] • Using acetate is not advantageous for improving performance of manure-fed MECs. • Cross-feeding lowers methane production performance during electromethanogenesis. • To produce similar CH 4 from manure as acetate, two times greater sCOD is required. • Model exoelectrogen Geobacter dominated the anodes of all manure-fed MECs. • Hydrogenotrophic Methanoculleus is abundant on the cathodes of manure-fed MECs. This study qualitatively assessed the impacts of different start-up strategies on the performance of methane (CH 4) production from cattle manure (CM) in electromethanogenic reactors. Single chamber MECs were operated with an applied voltage of 0.7 V and the impact of electrode acclimatization with a simple substrate, acetate (ACE) vs a complex waste, CM, was compared. Upon biofilm formation on the sole carbon source (ACE or CM), several MECs (ACE_CM and CM_ACE) were subjected to cross-feeding (switching substrate to CM or ACE) during the test period to evaluate the impact of the primary substrate. Even though there was twice as much peak current density via feeding ACE during biofilm formation, this did not translate into higher CH 4 production during the test period, when reactors were fed with CM. Higher or similar CH 4 production was recorded in CM_CM reactors compared to ACE_CM at various soluble chemical oxygen demand (sCOD) concentrations. Additionally, feeding ACE as primary substrate did not significantly impact either COD removals or coulombic efficiencies. On the other hand, the use of anaerobic digester (AD) seed as an inoculum in CM-fed MECs (CM_CM), relative to no inoculum added MECs (Blank), increased the initial CH 4 production rate by 45% and reduced the start-up time by 20%. In CM-fed MECs, Geobacter dominated bacterial communities of bioanodes and hydrogenotrophic methanogen Methanoculleus dominated archaeal communities of biocathodes. Community cluster analysis revealed the significance of primary substrate in shaping electrode biofilm; thus, it should be carefully selected for successful start-up of electromethanogenic reactors treating wastes. [ABSTRACT FROM AUTHOR]

[Display omitted] • Plate reactor design enables high-rate microbial electrosynthesis (MES). • High-rate electromethanogenesis obtained by M. maripaludis and mixed culture. • MES of acetate by T. kivui on par with glucose fermentation rates. • Acetate production rates by MES approach commercial gas fermentation rates. • Improved electron donor utilization by MES compared to classical biotechnology. Microbial electrosynthesis (MES) converts (renewable) electrical energy into CO 2 -derived chemicals including fuels. To achieve commercial viability of this process, improvements in production rate, energy efficiency, and product titer are imperative. Employing a compact plate reactor with zero gap anode configuration and NiMo-plated reticulated vitreous carbon cathodes substantially improved electrosynthesis rates of methane and acetic acid. Electromethanogenesis rates exceeded 10 L L–1 catholyte d–1 using an undefined mixed culture. Continuous thermophilic MES by Thermoanaerobacter kivui produced acetic acid at a rate of up to 3.5 g L−1 catholyte h−1 at a titer of 14 g/L , surpassing continuous gas fermentation without biomass retention and on par with glucose fermentation by T. kivui in chemostats. Coulombic efficiencies reached 80 %–90 % and energy efficiencies up to 30 % for acetate and methane production. The performance of this plate reactor demonstrates that MES can deliver production rates that are competitive with those of established biotechnologies. [ABSTRACT FROM AUTHOR]

Electromethanogenesis is an interesting next-generation technology to produce methane from CO2 and electricity by using methanogens. Iron-corroding methanogens might be of special interest for that application due to their natural ability for electron uptake. Methanococcus maripaludis Mic1c10 and KA1 were tested in bioelectrochemical systems. Strain Mic1c10 showed a 120% higher current density and an 84% higher methane production rate (16.2 mmol m−2 d−2) than the non-corrosive strain Methanococcus maripaludis S2, which was identified earlier as the best methane producer under the same experimental conditions. Interestingly, strain KA1 also showed a 265% higher current density than strain S2. Deposits at the cathodes were detected and analyzed, which were not described earlier. A comparative genome analysis between the corrosive methanogen and the S2 strain enables new insights into proteins that are involved in enhanced electron transfer. [ABSTRACT FROM AUTHOR]

Anaerobic digestion faces numerous challenges, including high CO 2 content in biogas and volatile fatty acids (such as propionate) accumulation in digestate. To address these issues, an up-flow dual-chamber electrocatalytic anaerobic bioreactor (UF-DC-EAB) was developed to enhance propionate degradation through microbial symbiosis while improving biogas quality via CO 2 electromethanogenesis. Under the extreme conditions with propionate as the primary carbon source at 6-h HRT, the UF-DC-EAB achieved a propionate removal efficiency of 72.1 ± 9.4 % and a faradaic efficiency of 25.5 ± 5.1 %. Microbial community analysis revealed an enrichment of acetoclastic methanogens (Methanosarcinales, 5.4 %) and syntrophic propionate-oxidizing bacteria (Syntrophobacterales, 13.9 %) in the anode, which facilitated propionate degradation. In the cathode, hydrogenotrophic methanogens (Methanobacterium, 13.6 %) and electroactive bacteria (Geobacter, 6.2 %) were predominant, further promoting CO 2 electromethanogenesis and biogas upgrading. Co-occurrence network and structural equation modeling indicated that the electrocatalytic regulation roused the intrinsic capability of the microbial community to oxidize propionate and provoked the occurrence of direct interspecies electron transfer (DIET) among the enriched functional microorganisms, by regulating the synthesis of key molecules like F 420 and cytochrome c in response to propionate-induced changes. The DIET-mediated syntropy increased the net energy output by 212.5 %. This study presents a novel electrochemical system combining CO 2 electromethanogenesis with propionate-rich digestate degradation, offering an efficient approach for anaerobic post-treatment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Methanogenic archaea play an important role in the global carbon cycle, as they catalyze the final step in anaerobic biomass decomposition to generate methane. This physiological trait has attracted much attention for the production of biogenic methane with methanogenic archaea as an alternative to fossil natural gas. Considerable progress has been made on the bioprocessing aspects for this purpose, and bioelectrochemical systems are considered to further optimize cost-effectiveness. Genetic tools for mesophilic methanogenic archaea are long available; however, more sophisticated methodology is still in its infancy. Thus, there is a requirement to develop further genetic tools. Moreover, biotechnologically relevant species are becoming genetically accessible only recently. However, the production of value-added products, such as isoprene, with methanogenic archaea has been demonstrated at low levels. In this perspective article, we discuss some of the recent developments on bioprocessing and genetic engineering strategies and provide a brief perspective on the biotechnological prospects of methanogenic archaea.

Carbon capture and utilization has been proposed as one strategy to combat global warming. Microbial electrolysis cells (MECs) combine the biological conversion of carbon dioxide (CO2) with the formation of valuable products such as methane. This study was motivated by the surprising gap in current knowledge about the utilization of real exhaust gas as a CO2 source for methane production in a fully biocatalyzed MEC. Therefore, two steel mill off-gases differing in composition were tested in a two-chamber MEC, consisting of an organic substrate-oxidizing bioanode and a methane-producing biocathode, by applying a constant anode potential. The methane production rate in the MEC decreased immediately when steel mill off-gas was tested, which likely inhibited anaerobic methanogens in the presence of oxygen. However, methanogenesis was still ongoing even though at lower methane production rates than with pure CO2. Subsequently, pure CO2 was studied for methanation, and the cathodic biofilm successfully recovered from inhibition reaching a methane production rate of 10.8 L m−2d−1. Metagenomic analysis revealed Geobacter as the dominant genus forming the anodic organic substrate-oxidizing biofilms, whereas Methanobacterium was most abundant at the cathodic methane-producing biofilms.

Dark fermentation of cheese whey (CW) for the production of biohydrogen generates an acidic effluent, containing high concentrations of volatile fatty acids, which needs to be further treated before disposal and possibly further valorised. This study develops a dual-chamber Microbial Electrolysis Cell (MEC) that achieves simultaneously the reduction of the organic content of this effluent to environmentally acceptable levels, along with bio-electrochemical reduction of CO 2 to CH 4. The MEC was operated for 140 days and the effect of the following conditions on the MEC performance was examined: (a) the feed concentration of the acidic fermentate (in the range 6–81 g COD /L), (b) the conductivity of the feed modified via KCl addition (range 2–22 mS/cm), (c) the MEC operation mode (with or without catholyte renewal) and (d) the solids content (modified via CW filtration prior to its use). The results showed that high COD removal (>95 %) was achieved in all cases, along with a CH 4 production of up to 1.1 mmol/g CODconsumed. The best performance of the cell was obtained for a feed COD concentration of ∼30 g COD /L and a feed conductivity of ∼15 mS/cm; these conditions resulted in a COD removal exceeding 99 %, a CH 4 production of 1.1 mmol CH4 /g CODconsumed and a net energy production of 15.8 % compared to the energy demand of the system. The electrochemical study of the system revealed that higher and lower feed COD concentrations were characterized by higher internal resistances. The results indicate that the MEC can be exploited for further treatment and valorization of a high-strength effluent along with the production of CH 4 with an energy surplus, as an efficient waste-to-energy technology. [Display omitted] • High organic load removal was achieved in all cases (>95 % COD removal). • Energy gain reached up to 199 % relative to the expenditure due to applied potential. • Optimal performance was obtained at moderate conditions (30 g COD /L, 15 mS/cm). • Catholyte renewal enables treatment of the undiluted (63 g COD /L) waste. • Fermentative bacteria contained in the acidified cheese whey inhibit MEC operation. [ABSTRACT FROM AUTHOR]

BACKGROUND Biogas can be upgraded to biomethane, which can be used as vehicle fuel and natural gas substitute. Bioelectrochemical biogas upgrade is an innovative alternative to energy‐consuming physicochemical processes and bio‐upgrade methods which require H2 supply. Bioelectrochemical biogas upgrade is conducted by methanogenic microorganisms that convert CO2 into CH4, in the biocathode of a bioelectrochemical system (BES), using electric current as energy source. The aim of the present work was to study the efficiency of an H‐type BES in the conversion of CO2 into CH4, by applying different potentials at the electromethanogenic biocathode. RESULTS: The H‐type BES was operated in a three‐electrode configuration (working: graphite rod; counter: Pt/Ti; reference: Ag/AgCl) with a potentiostat, which set the biocathode's potential initially at −0.7 V versus a standard hydrogen electrode (SHE) and monitored the current demand. Based on cyclic voltammetry runs, a highly electroactive methanogenic biocathode was developed in a short time. The methane production rate (MPR) at a cathode potential of −0.7 V versus SHE was 31.1 mmol m−2 d−1, with an electron capture efficiency of 77.6%. The efficiency of the BES was reduced by applying a potential of −0.5 V versus SHE at the biocathode, resulting in negligible CH4 production. The BES achieved its maximum performance at a potential of −0.9 V versus SHE with a MPR of 53.8 mmol m−2 d−1 and an electron capture efficiency of 86%. The CO2 consumption rate achieved was 0.8 mmol d−1. CONCLUSIONS: The H‐type BES achieved an effective biolectrochemically driven methane production, while the biocathode electroactive behavior was evaluated during the whole operation of the system. © 2021 Society of Chemical Industry (SCI). [ABSTRACT FROM AUTHOR]

The ability of microorganisms to carry out interspecies electron transfer during the degradation of organic substances under anaerobic conditions opens up new possibilities for a controlled increase in the efficiency of the methanogenic decomposition of organic waste. This review presents the main principles of the effects of a direct electric current on the anaerobic degradation of organic substances, process parameters, changes in the composition of the microbial community, and factors affecting the optimization of the hybrid systems comprising microbial electrolysis cell (MEC) and anaerobic digester (AD), i.e., the performance of the MEC-AD system. The research in this field has been analyzed for the subsequent application of electromethanogenesis, which represents a new energy-efficient biotechnology for anaerobic wastewater treatment and organic waste digestion. [ABSTRACT FROM AUTHOR]

Anaerobic digestion is a traditional method of producing methane-containing biogas by utilizing the methanogenic conversion of organic matter like agricultural waste and animal excreta. Recently, the application of microbial electrolysis cell (MECs) technology to a traditional anaerobic digestion system has been extensively studied to find new opportunities in increasing wastewater treatability and methane yield and producing valuable chemicals. The finding that both anodic and cathodic bacteria can synthesize methane has led to the efforts of optimizing multiple aspects like microbial species, formation of biofilms, substrate sources and electrode surface for higher production of the combustible compound. MECs are very fascinating because of its ability to uptake a wide variety of raw materials including untreated wastewater (and its microbial content as biocatalysts). Extensive work in this field has established different systems of MECs for hydrogen production and biodegradation of organic compounds. This review is dedicated to explaining the operating principles and mechanism of the MECs for electromethanogenesis using different biochemical pathways. Emphasis on single- and double-chambered MECs along with reactor components is provided for a comprehensive description of the technology. Methane production using hydrogen evolution reaction and nanocatalysts has also been discussed. [ABSTRACT FROM AUTHOR]

Microbial electrochemical system (MES) for enhancing methane production has gained significant interest during the recent years, but the practical applications of MES are still far away due to several limitations such as low efficiency of cathodic electrochemical kinetics. In this study, novel porous reduced-graphene oxide/hollow titania (rGO/TiO 2) was successfully synthesized to be used as cathode catalyst for promoting electrochemical reduction of CO 2 to methane. The MES operation with rGO/TiO 2 catalyst exhibited 15.4% higher methane yield (0.383 ± 0.01 LCH 4 /gCOD) and 13.4% higher production rate (152.38 mL/L.d) compared to control MES with bare carbon cloth cathode. The MES-rGO/TiO 2 produced around 33% higher in total Coulomb at 3837.9 ± 351.5C compared to the pristine cathode at 2887.92 ± 254.6C. Substrate degradation and volatile fatty acids conversion were significantly improved in the presence of rGO/TiO 2 catalyst. By using cyclic voltammetry and electrochemical impedance spectroscopy analysis, rGO/TiO 2 was proved to ease the electron transfer efficiency of working cathode for the conversion of electron to methane. The results suggest that porous rGO/TiO 2 can be a promising cathode catalyst to upgrade the performance of a scalable methane-producing MES-AD system. • Porous rGO and hollow TiO 2 was successfully synthesized and applied as catalyst of MES cathode. • Catalyzed MES enhanced 20% and 33% methane accumulation and coulomb generation, respectively. • rGO/TiO 2 eased the decomposition of substrate and VFAs for a better methane production rate. • rGO/TiO 2 enhanced catalytic activity and lowered charge transfer resistance of working cathode. [ABSTRACT FROM AUTHOR]

Two-stage anaerobic digestion (AD) is a promising method of converting organic waste into clean and sustainable energy. This work aimed to study the efficiency of a two-stage AD system with the production of hydrogen at the first acidogenic stage and methane in an electromethanogenic reactor. Two types of biocathodes based on carbon cloth were used in the electromethanogenic reactor: with and without retention of biomass on the electrode surface. A high applied voltage continuously supplied to the pair of electrodes was automatically maintained at 2.5 V. Hydrogen yield (0.11 NL/g volatile solids (VS) init or 2 mol H 2 /mol hexose) and hydrogen content in biogas (52%) were relatively high, even despite the extremely low pH (∼4.0). Improved retention of biomass on the surface of the carbon cloth-based biocathode led to greater stability of the AD process (no water electrolysis was observed) and a significant increase in the efficiency of electromethanogenesis, including the methane yield (by 40.5% up to 0.39 NL/g VS init), volumetric methane production rate (by 38.8% up to 1.16 NL/L/d) and current density (by 233% up to 0.56 A/m2). • T= 57.5 °C and pH ∼4 completely suppressed methanogenesis in the acidogenic reactor. • 2 mol H2/mol glucose during continuous dark fermentation of OF-MSW is achieved. • Better biomass attachment to the biocathode increased the current density by 233%. • Increase in CH4 yield by 40.5% and volumetric CH4 production rate by 38.8%. • A physical barrier is an effective tool to retain biomass on the biocathode surface. [ABSTRACT FROM AUTHOR]

Electromethanogenesis refers to the process whereby methanogens utilize current for the reduction of CO2 to CH4. Setting low cathode potentials is essential for this process. In this study, we tested if magnetite, an iron oxide mineral widespread in the environment, can facilitate the adaptation of methanogen communities to the elevation of cathode potentials in electrochemical reactors. Two-chamber electrochemical reactors were constructed with inoculants obtained from paddy field soil. We elevated cathode potentials stepwise from the initial -0.6 V versus the standard hydrogen electrode (SHE) to -0.5 V and then to -0.4 V over the 130 days of acclimation. Only weak current consumption and CH4 production were observed in the bioreactors without magnetite. However, significant current consumption and CH4 production were recorded in the magnetite bioreactors. The robustness of electroactivity of the magnetite bioreactors was not affected by the elevation of cathode potentials from -0.6 V to -0.4 V. However, the current consumption and CH4 production were halted in the bioreactors without magnetite when the cathode potentials were elevated to -0.4 V. Methanogens related to Methanospirillum were enriched on the cathode surfaces of magnetite bio-reactors at -0.4 V, while Methanosarcina relatively dominated in the bioreactors without magnetite. Methanobacterium also increased in the magnetite bioreactors but stayed off electrodes at -0.4 V. Apparently, the magnetite greatly facilitates the development of biocathodes, and it appears that with the aid of magnetite, Methanospirillum spp. can adapt to the high cathode potentials, performing efficient electromethanogenesis. IMPORTANCE Converting CO2 to CH4 through bioelectrochemistry is a promising approach to the development of green energy biotechnology. This process, however, requires low cathode potentials, which entails a cost. In this study, we tested if magnetite, a conductive iron mineral, can facilitate the adaptation of methanogens to the elevation of cathode potentials. In two-chamber reactors constructed by using inoculants obtained from paddy field soil, biocathodes developed robustly in the presence of magnetite, whereas only weak activities in CH4 production and current consumption were observed in the bioreactors without magnetite. The elevation of cathode potentials did not affect the robustness of electroactivity of the magnetite bioreactors over the 130 days of acclimation. Methanospirillum strains were identified as the key methanogens associated with the cathode surfaces during the operation at high potentials. The findings reported in this study shed new light on the adaptation of methanogen communities to the elevated cathode potentials in the presence of magnetite. [ABSTRACT FROM AUTHOR]

Electromethanogenesis is an interesting next-generation technology to produce methane from CO2 and electricity by using methanogens. Iron-corroding methanogens might be of special interest for that application due to their natural ability for electron uptake. Methanococcus maripaludis Mic1c10 and KA1 were tested in bioelectrochemical systems. Strain Mic1c10 showed a 120% higher current density and an 84% higher methane production rate (16.2 mmol m−2 d−2) than the non-corrosive strain Methanococcus maripaludis S2, which was identified earlier as the best methane producer under the same experimental conditions. Interestingly, strain KA1 also showed a 265% higher current density than strain S2. Deposits at the cathodes were detected and analyzed, which were not described earlier. A comparative genome analysis between the corrosive methanogen and the S2 strain enables new insights into proteins that are involved in enhanced electron transfer.

Electromethanogenesis has emerged as a biological branch of Power-to-X technologies that implements methanogenic microorganisms, as an alternative to chemical Power-to-X, to convert electrical power from renewable sources, and CO 2 into methane. Unlike biomethanation processes where CO 2 is converted via exogenously added hydrogen, electromethanogenesis occurs in a bioelectrochemical set-up that combines electrodes and microorganisms. Thereby, mixed, or pure methanogenic cultures catalyze the reduction of CO 2 to methane via reducing equivalents supplied by a cathode. Recent advances in electromethanogenesis have been driven by interdisciplinary research at the intersection of microbiology, electrochemistry, and engineering. Integrating the knowledge acquired from these areas is essential to address the specific challenges presented by this relatively young biotechnology, which include electron transfer limitations, low energy and product efficiencies, and reactor design to enable upscaling. This review approaches electromethanogenesis from a multidisciplinary perspective, putting emphasis on the extracellular electron uptake mechanisms that methanogens use to obtain energy from cathodes, since understanding these mechanisms is key to optimize the electrochemical conditions for the development of these systems. This work summarizes the direct and indirect extracellular electron uptake mechanisms that have been elucidated to date in methanogens, along with the ones that remain unsolved. As the study of microbial corrosion, a similar bioelectrochemical process with Fe0 as electron source, has contributed to elucidate different mechanisms on how methanogens use solid electron donors, insights from both fields, biocorrosion and electromethanogenesis, are combined. Based on the repertoire of mechanisms and their potential to convert CO 2 to methane, we conclude that for future applications, electromethanogenesis should focus on the indirect mechanism with H 2 as intermediary. By summarizing and linking the general aspects and challenges of this process, we hope that this review serves as a guide for researchers working on electromethanogenesis in different areas of expertise to overcome the current limitations and continue with the optimization of this promising interdisciplinary technology. • Electromethanogenesis is a promising technology being optimized at the lab scale. • Interdisciplinary work is required to overcome the system limitations for upscaling. • New mechanisms on electron uptake have been elucidated in methanogens. • Electrochemical parameters must suit the methanogenic electron uptake mechanisms. • Non-electrotrophic methanogens are key biocatalysts for this technology. [ABSTRACT FROM AUTHOR]

Bioelectrochemical power-to-gas represents a novel solution for electrical energy storage, currently under development. It allows storing renewable energy surplus in the form of methane (CH4), while treating wastewater, therefore bridging the electricity and natural gas (and wastewater) grids. The technology can be coupled with membrane contactors for carbon dioxide (CO2) capture, dissolving the CO2 in wastewater before feeding it to the bioelectrochemical system. This way, the integrated system can achieve simultaneous carbon capture and energy storage objectives, in the scenario of a wastewater treatment plant application. In this study, such technology was developed in a medium-scale prototype (32 L volume), which was operated for 400 days in different conditions of temperature, voltage and CO2 capture rate. The prototype achieved the highest CH4 production rate (147 ± 33 L m–3 d–1) at the lowest specific energy consumption (1.0 ± 0.3 kWh m–3 CH4) when operated at 25°C and applying a voltage of 0.7 V, while capturing and converting 22 L m–3 d–1 of CO2. The produced biogas was nearer to biomethane quality (CH4 > 90% v/v) when CO2 was not injected in the wastewater. Traces of hydrogen (H2) in the biogas, detectable during the periods of closed electrical circuit operation, indicated that hydrogenotrophic methanogenesis was taking place at the cathode. On the other hand, a relevant CH4 production during the periods of open electrical circuit operation confirmed the presence of acetoclastic methanogenic microorganisms in the microbial community, which was dominated by the archaeal genus Methanothrix (Euryarchaeota). Different operational taxonomic units belonging to the bacterial Synergistes phylum were found at the anode and the cathode, having a potential role in organic matter degradation and H2 production, respectively. In the panorama of methanation technologies currently available for power-to-gas, the performances of this bioelectrochemical prototype are not yet competitive, especially in terms of volumetric CH4 production rate and power density demand. However, the possibility to obtain a high-quality biogas (almost reaching biomethane quality standards) at a minimal energy consumption represents a potentially favorable business scenario for this technology.

Electron‐shuttling molecules (ESMs), natural or synthetic, are utilized by microorganisms as electron acceptors or donors to facilitate electron transfer. In this study, five ESMs, namely anthraquinone‐2‐carboxylic acid (AQC), 9,10‐anthraquinone‐2‐sulfonicacid (AQS), 9,10‐anthraquinone‐2,6‐disulfonic acid (AQDS), Neutral red, and Thionin, were selected to assess their effects on electromethanogenesis under different electrochemical potentials and concentrations. Results showed that the rate of methanogenesis achieved in the presence of AQC was 7.4 times higher than that of the control (without ESMs) at −850 mV (vs. Ag/AgCl). The effectiveness on methanogenesis followed AQC, Neutral Red, AQS, AQDS, and Thionin in a decreasing order. Compared with the control, the addition of ESMs did not affect the biomass of methanogens significantly. Meanwhile, qPCR analysis of the ccdA gene indicated that the abundance of the Cytochrome c gene and the extent of CO2 reduction to methane correlated positively. The promoting effect of the selective ESMs on methanogenesis was mainly related to their electron transfer capabilities. [ABSTRACT FROM AUTHOR]

Power-to-Gas technologies are high-capacity systems, which can be used to optimise the use of renewable energy to meet energy demands. Among them, Power-to-Methane (PtM) stands out due to the ease of storage and use of the produced methane. However, its total storing efficiency (Power-to-Methane-to-Power) is likely still low as there are various losses. This paper presents an overview of PtM improvement through the utilisation of low-temperature waste heat produced upon the two steps by converting power to gas, namely electrolysis and methanation. An organic Rankine cycle, Stirling engine, and thermoelectric generator were chosen as promising technologies that could be implemented to recover the waste heat and improve the PtM system. Several experimental studies of each technology were reviewed. Moreover, some technological and economic surveys are described and discussed. At the end of the article, the study discussed the direction of further research and development for waste heat recovery in the system to increase the competitiveness of the PtM system and its efficiency. • Some possible Power-to-Methane configurations are described. • Power-to-Methane offers high energy density and long-term capabilities. • An improvement of Power-to-Methane based on waste heat recovery is discussed. • Selected promising waste heat recoveries below 100.0 °C are described and compared. • Several techno-economic parameters for assessing the improvement are described. [ABSTRACT FROM AUTHOR]

Microbial electrosynthesis (MES) has been gaining considerable interest as the next step in the evolution of microbial electrochemical technologies. Understanding the niche biocathode environment and microbial community is critical for further developing this technology as the biocathode is key to product formation and efficiency. MES is generally operated to enrich a specific functional group (e.g., methanogens or homoacetogens) from a mixed-culture inoculum. However, due to differences in H2 and CO2 availability across the cathode surface, competition and syntrophy may lead to overall variability and significant beta-diversity within and between replicate reactors, which can affect performance reproducibility. Therefore, this study aimed to investigate the distribution and potential spatial variability of the microbial communities in MES methanogenic biocathodes. Triplicate methanogenic biocathodes were enriched in microbial electrolysis cells for 5 months at an applied voltage of 0.7 V. They were then transferred to triplicate dual-chambered MES reactors and operated at -1.0 V vs. Ag/AgCl for six batches. At the end of the experiment, triplicate samples were taken at different positions (top, center, bottom) from each biocathode for a total of nine samples for total biomass protein analysis and 16S rRNA gene amplicon sequencing. Microbial community analyses showed that the biocathodes were highly enriched with methanogens, especially the hydrogenotrophic methanogen family Methanobacteriaceae, Methanobacterium sp., and the mixotrophic Methanosarcina sp., with an overall core community representing > 97% of sequence reads in all samples. There was no statistically significant spatial variability (p > 0.05) observed in the distribution of these communities within and between the reactors. These results suggest deterministic community assembly and indicate the reproducibility of electromethanogenic biocathode communities, with implications for larger-scale reactors.

Direct electron uptake by prokaryotes is a recently described mechanism with a potential application for energy and CO2 storage into value added chemicals. Members of Methanosarcinales, an environmentally and biotechnologically relevant group of methanogens, were previously shown to retrieve electrons from an extracellular electrogenic partner performing Direct Interspecies Electron Transfer (DIET) and were therefore proposed to be electroactive. However, their intrinsic electroactivity has never been examined. In this study, we tested two methanogens belonging to the genus Methanosarcina, M. barkeri, and M. horonobensis, regarding their ability to accept electrons directly from insoluble electron donors like other cells, conductive particles and electrodes. Both methanogens were able to retrieve electrons from Geobacter metallireducens via DIET. Furthermore, DIET was also stimulated upon addition of electrically conductive granular activated carbon (GAC) when each was co-cultured with G. metallireducens. However, when provided with a cathode poised at −400 mV (vs. SHE), only M. barkeri could perform electromethanogenesis. In contrast, the strict hydrogenotrophic methanogen, Methanobacterium formicicum, did not produce methane regardless of the type of insoluble electron donor provided (Geobacter cells, GAC or electrodes). A comparison of functional gene categories between the two Methanosarcina showed differences regarding energy metabolism, which could explain dissimilarities concerning electromethanogenesis at fixed potentials. We suggest that these dissimilarities are minimized in the presence of an electrogenic DIET partner (e.g., Geobacter), which can modulate its surface redox potentials by adjusting the expression of electroactive surface proteins.

Microbial electrosynthesis (MES) has been gaining considerable interest as the next step in the evolution of microbial electrochemical technologies. Understanding the niche biocathode environment and microbial community is critical for further developing this technology as the biocathode is key to product formation and efficiency. MES is generally operated to enrich a specific functional group (e.g., methanogens or homoacetogens) from a mixed-culture inoculum. However, due to differences in H2 and CO2 availability across the cathode surface, competition and syntrophy may lead to overall variability and significant beta-diversity within and between replicate reactors, which can affect performance reproducibility. Therefore, this study aimed to investigate the distribution and potential spatial variability of the microbial communities in MES methanogenic biocathodes. Triplicate methanogenic biocathodes were enriched in microbial electrolysis cells for 5 months at an applied voltage of 0.7 V. They were then transferred to triplicate dual-chambered MES reactors and operated at -1.0 V vs. Ag/AgCl for six batches. At the end of the experiment, triplicate samples were taken at different positions (top, center, bottom) from each biocathode for a total of nine samples for total biomass protein analysis and 16S rRNA gene amplicon sequencing. Microbial community analyses showed that the biocathodes were highly enriched with methanogens, especially the hydrogenotrophic methanogen family Methanobacteriaceae, Methanobacterium sp., and the mixotrophic Methanosarcina sp., with an overall core community representing > 97% of sequence reads in all samples. There was no statistically significant spatial variability (p > 0.05) observed in the distribution of these communities within and between the reactors. These results suggest deterministic community assembly and indicate the reproducibility of electromethanogenic biocathode communities, with implications for larger-scale reactors. [ABSTRACT FROM AUTHOR]

Hydrothermal carbonization (HTC) is a biomass conversion process that generates a CO 2 -rich gaseous phase that is commonly released directly into the atmosphere. Microbial electromethanogeneis (EM) can potentially use this off-gas to convert the residual CO 2 into CH 4, thus avoiding GHG emissions while adding extra value to the overall bioprocess. In the present work, the HTC gas phase was fed to two mixed-culture biocathodes (replicates) polarized at −1.0V vs. Ag/AgCl. Compared to pure CO 2 , HTC gas had a marked negative effect on the process, decreasing current density by 61%, while maximum CH₄ yield contracted up to 50%. HTC also had an unequal impact on the cathodic microbial communities, with the methanogenic hydrogenotrophic archaea Methanobacteriaceae experiencing the largest decline. Despite that, the present study demonstrates that HTC can be used in EM as a raw material to produce a biogas with a methane content of up to 70%. • Electromethanogenesis can convert hydrothermal carbonization off-gas into methane. • HTC off-gas had a marked negative effect on the process in comparison to pure CO 2. • qPCR analyses revealed a larger impact on methanogenic communities. • The presence of CO in the HTC off-gas would explain the poorer performance. [ABSTRACT FROM AUTHOR]

Anaerobic digestion process can be improved in combination with bioelectrochemical systems in order to recover energy and resources from digestates. An electromethanogenic microbial electrolysis cell (MEC) coupled to an ammonia recovery system based on hydrophobic membranes (ARS-HM) has been developed in order to recover ammonia, reduce organic matter content and upgrade biogas from digested pig slurry. A lab-scale dual-chamber MEC was equipped with a cation exchange membrane (CEM) and ARS with a hydrophobic membrane in the catholyte recirculation loop, to promote ammonia migration and absorption in an acidic solution. On the other hand, an electromethanogenic biofilm was developed in the biocathode to promote the transformation of CO2 into methane. The average nitrogen transference through the CEM was of 0.36 gN m−2 h−1 with a removal efficiency of 31%, with the ARS-HM in the catholyte recirculation loop. The removal of ammonia from the cathode compartment helped to maintain a lower pH value for the electromethanogenic biomass (7.69 with the ARS-HM, against 8.88 without ARS-HM) and boosted methane production from 50 L m−3 d−1 to 73 L m−3 d−1. Results have shown that the integration of an electromethanogenic MEC with an ARS-HM allows for the concomitant recovery of energy and ammonia from high strength wastewater digestates.

In subsurface anoxic environments, microbial communities generally produce methane as an end-product to consume organic compounds. This metabolic function is a source of biogenic methane in coastal natural gas aquifers, submarine mud volcanoes, and methane hydrates. Within the methanogenic communities, hydrogenotrophic methanogens, and syntrophic bacteria are converting volatile fatty acids to methane syntrophically via interspecies hydrogen transfer. Recently, direct interspecies electron transfer (DIET) between fermentative/syntrophic bacteria and electrotrophic methanogens has been proposed as an effective interspecies metabolite transfer process to enhance methane production. In this study, in order to stimulate the DIET-associated methanogenic process at deep biosphere-aquifer systems in a natural gas field, we operated a bioelectrochemical system (BES) to apply voltage between an anode and a cathode. Two single-chamber BESs were filled with seawater-based formation water collected from an onshore natural gas well, repeatedly amended with acetate, and operated with 600 mV between electrodes for 21 months, resulting in a successful conversion of acetate to methane via electrical current consumption. One reactor yielded a stable current of ~200 mA/m2 with a coulombic efficiency (CE) of >90%; however, the other reactor, which had been incidentally disconnected for 3 days, showed less electromethanogenic activity with a CE of only ~10%. The 16S rRNA gene-based community analyses showed that two methanogenic archaeal families, Methanocalculaceae and Methanobacteriaceae, were abundant in cathode biofilms that were mainly covered by single-cell-layered biofilm, implicating them as key players in the electromethanogenesis. In contrast, family Methanosaetaceae was abundant at both electrodes and the electrolyte suspension only in the reactor with less electromethanogenesis, suggesting this family was not involved in electromethanogenesis and became abundant only after the no-electron-flow event. The anodes were covered by thick biofilms with filamentous networks, with the family Desulfuromonadaceae dominating in the early stage of the operation. The family Geobacteraceae (mainly genus Geoalkalibacter) became dominant during the longer-term operation, suggesting that these families were correlated with electrode-respiring reactions. These results indicate that the BES reactors with voltage application effectively activated a subsurface DIET-related methanogenic microbiome in the natural gas field, and specific electrogenic bacteria and electromethanogenic archaea were identified within the anode and/or cathode biofilms.

Graphical abstract Highlights • Design of bubble column reactor for various types of bioelectrochemical processes. • First use of a highly flexible bubble column reactor in bioelectrochemistry. • Proof of principle was carried out with two different process. • Reactor characterization was done allowing better comparison with other BES. • Suggestion of scale-up parameters for bioelectrochemical systems. Abstract In times of energy revolution, bioelectrochemistry is a growing field of research, either for the generation of electrical energy from organic substrates or the use of electrical energy to produce various products. By now, this technology is on the turning point from lab scale to industrial applications. Unfortunately, there is still a lack of well characterized, scalable reactor systems that are capable of hosting different bioelectrochemical processes, linking lab scale research to industrial application. In this paper, we introduce a two-chamber bioelectrochemical bubble-column reactor (one liter working volume), which can be used as microbial fuel cell as well as for microbial electrosynthesis and is especially advantageous for processes with gaseous substrates. It is designed flexible in terms of electrode material and area, membrane material and area, and capable of hosting continuous processes. It is a promising replacement of lab-scale H-cells for wider screening possibilities with regard to industrial applications. We characterized the reactor by giving key values such as k L a and gas hold up, and suggest scale-up parameters. These are, for example, dimensionless numbers like Reynolds and Wagner number and different ratios that should be kept constant during scale-up. Therefore, this paper can be a guideline for the development and scale-up of bioelectrochemical systems. [ABSTRACT FROM AUTHOR]

Each carbon-based material, due to the discrepancy in critical properties, has distinct capability to enrich electroactive microbes able to electrosynthesize methane from CO 2 . To optimize electromethanogenesis process, this study physically prepared and examined several carbon-based cathode materials: carbon stick (CS), CS twined by Ti wire (CS-Ti) or covered with carbon fiber (CS-CF), graphite felt (CS-GF) and carbon cloth (CS-CC). CS-GF electrode had constantly stable methane production (75.8 mL/L/d at −0.9 V vs. Ag/AgCl) while CS-CC showed a suppressed performance over time caused by the desposition of inorganic shell. Electrode material properties affected biofilms growth, cell-electrode contact behaviors and electron exchange. Methane formation with CS-CC biocathode was H 2 -concnetration dependent; CS-GF cathode possessed high antifouling properties and extensive space, enriching the microorganisms capable of catalyzing electromethanogenesis through more efficient non-H 2 route. This study re-interpreted the application potentials of carbon-based materials in CO 2 electroreduction and electrofuel recovery, providing valuable guidance for materials’ selection. [ABSTRACT FROM AUTHOR]

The integration of anaerobic digestion (AD) and a microbial electrolysis cell (MEC) with an electromethanogenic biocathode is proposed to increase the stability and robustness of the AD process against organic and nitrogen overloads; to keep the effluent quality; to recover ammonium; and to upgrade the biogas. A thermophilic lab-scale AD, fed with pig slurry, was connected in series with the bioanode compartment of a two-chambered MEC. In turn, the biocathode of the MEC was poised at −800 mV vs Standard Hydrogen Electrode and fed with CO 2 to increase the methane production of the system. After doubling its organic and nitrogen loading rate, the AD operation became stable thanks to the connection of a recirculation loop with the MEC effluent. Ammonium removal in the anode compartment of the MEC achieved 14.46 g N-NH 4 + m −2 d −1 , while obtaining on average 79 L CH 4 m −3 d −1 through the conversion of CO 2 in the cathode compartment. The microbial analysis showed that methylotrophic Methanossiliicoccaceae family ( Methanomassiliicoccus genus) was the most abundant among the metabolically active archaea in the AD during the inhibited state; while, on the cathode, Methanobacteriaceae family ( Methanobrevibacter and Methanobacterium genus) shared dominance with Methanomassiliicoccaceae and Methanotrichaceae families ( Methanomassiliicoccus and Methanothrix genus, respectively). [ABSTRACT FROM AUTHOR]

Electromethanogenesis is a form of electrobiofuel production through a microbial electrolysis cell (MEC) where methane (CH 4 ) is directly produced from an electrical current and carbon dioxide (CO 2 ) using a cathode. With the aim of maximizing methanogenesis in an MEC, this study utilized granular activated carbon (GAC) and a transition metal catalyst to fabricate nickel (Ni) nanoparticle (NP)-loaded GAC (Ni NP/GAC) composites and incorporated these into MECs. In this set-up, GAC acted as the main electrical conduit for direct interspecies electron transfer (DIET) between exoelectrogens and methanogenic electrotrophs, and the Ni NPs served as a catalyst to further improve microbe-to-GAC electron transfer. The Ni NP/GAC-composites were prepared using two different methods (microwave irradiation and solution plasma ionization). The Ni NPs were determined to be well doped on the GAC surface according to a field emission scanning electron microscope (FE-SEM) and energy-dispersive X-ray (EDX) spectroscopy analysis. Adding GAC into MECs improved CH 4 production. The Ni NP/GAC composites prepared by solution plasma ionization showed the highest CH 4 production (20.7 ml), followed by the Ni NP/GAC composite prepared by microwave irradiation (19.6 ml), bare GAC (15.6 ml), and GAC-free control (9.6 ml). In the methanogenic MECs, 40.6% of CH 4 was produced from an electrode reaction (i.e., reduction of CO 2 to CH 4 ), and the remaining 59.4% was generated by nonelectrode reactions. [ABSTRACT FROM AUTHOR]

Functioning biocathodes are essential for electromethanogenesis. This study investigated the development of a biocathode from non-acclimated anaerobic sludge in an electromethanogenesis cell at a cathode potential of −0.7 V (vs. standard hydrogen electrode) over four cycles of repeated batch operations. The CO 2 -to-CH 4 conversion rate increased (to 97.7%) while the length of the lag phase decreased as the number of cycles increased, suggesting that a functioning biocathode developed during the repeated subculturing cycles. CO 2 -resupply test results suggested that the biocathode catalyzed the formation of CH 4 via both direct and indirect (H 2 -mediated) electron transfer mechanisms. The biocathode archaeal community was dominated by the genus Methanobacterium , and most archaeal sequences (>89%) were affiliated with Methanobacterium palustre . The bacterial community was dominated by putative electroactive bacteria, with Arcobacter , which is rarely observed in biocathodes, forming the largest population. These electroactive bacteria were likely involved in electron transfer between the cathode and the methanogens. [ABSTRACT FROM AUTHOR]

Toward applications of bio-electrochemical systems in industrial processes and extreme environments, electromethanogenesis under high-pressure conditions was examined. Stainless-steel single-chamber reactors specifically designed to examine bio-electrochemical reactions under pressurized conditions were inoculated with thermophilic microorganisms originated from an oilfield formation water. The reactors were incubated at 5 MPa, 55°C in fed-batch operational mode with an applied voltage of 0.7 V. In the first few fed-batch cycles, hydrogen was mainly produced. After the third cycle, however, the reactors produced only methane simultaneously with current generation. The methane-production rate of the reactors showed an applied-voltage dependence and increased from 34.9 to 168.4 mmol m −2 day −1 with an increase in the applied voltage from 0.4 to 0.9 V. The efficiency of capturing electrons in the produced methane on average exceeded 70% with the applied voltage of 0.4 V or higher. Cyclic voltammetry further confirmed abilities of the bioelectrodes to catalyze electrochemical reactions at 5 MPa. Performance of the electromethanogenesis system was not altered under lower pressure conditions (1.2 and 2.5 MPa). An exoelectrogenic bacterium affiliated with the genus Thermincola and a methanogen belonging to the genus Methanothermobacter were detected as the dominant species in the bioanode and biocathode microbiotas, respectively. Thus, our results indicated that electromethanogenesis systems could be developed and operated under highly-pressurized conditions, suggesting that applications of the bio-electrochemical system in high-pressure environments (including high-temperature subsurface reservoirs) can be technically feasible. [ABSTRACT FROM AUTHOR]

The dispersion of granules in upflow anaerobic sludge blanket (UASB) reactor represents a critical technical issue in methanolic wastewater treatment. In this study, the potentials of coupling a microbial electrolysis cell (MEC) into an UASB reactor for improving methanolic wastewater biodegradation, long-term process stability and biomethane recovery were evaluated. The results indicated that coupling a MEC system was capable of improving the overall performance of UASB reactor for methanolic wastewater treatment. The combined system maintained the comparatively higher methane yield and COD removal efficiency over the single UASB process through the entire process, with the methane production at the steady-state conditions approaching 1504.7 ± 92.2 mL-CH 4 L − 1 -reactor d − 1 , around 10.1% higher than the control UASB (i.e. 1366.4 ± 71.0 mL-CH 4 L − 1 -reactor d − 1 ). The further characterizations verified that the input of external power source could stimulate the metabolic activity of microbes and reinforced the EPS secretion. The produced EPS interacted with Fe 2+/3+ liberated during anodic corrosion of iron electrode to create a gel-like three-dimensional [-Fe-EPS-] n matrix, which promoted cell-cell cohesion and maintained the structural integrity of granules. Further observations via SEM and FISH analysis demonstrated that the use of bioelectrochemical stimulation promoted the growth and proliferation of microorganisms, which diversified the degradation routes of methanol, convert the wasted CO 2 into methane and accordingly increased the process stability and methane productivity. [ABSTRACT FROM AUTHOR]

Electromethanogenesis (EM) is a reaction in a bio-electrochemical system (BES) in which microorganisms catalyse the reduction of CO 2 to methane by electric current at the cathode. We have proposed a novel application of EM combined with CO 2 Capture and Storage (CCS), in which geologically-sequestrated CO 2 is reduced to methane using electricity from variable renewables. To develop this technology, further investigation and establishment of the mathematical model are indispensable. In this study, experimental and mathematical analyses were conducted to develop mathematical model. A mathematical model for EM is developed based on BES models constructed in previous studies. As a result of mathematical analysis, it is suggested that EM reaction is dominated by the direct pathway at high cathode potential, and the methane production rate is proportional to the electrical current generated in the system. To calculate methane production rate via the indirect pathway requires measurement of microorganism concentration, and it will enable completion of mathematical model. Moreover, to examine the practical application of EM, a scale-up experiment was conducted in fed-batch mode using a 3 L volume reactor. As electrode material, carbonized coconut shells were chosen due to their large surface area, good biocompatibility, and good chemical stability with relatively low cost. Thermophilic microorganisms originated from a subsurface formation (a depleted petroleum reservoir) were inoculated in the reactor and incubated at 55 °C with applied voltages of 1.0 V or 0.7 V. The maximum CH 4 production rate was 340 mmol m -3 day -1 with current-capture efficiency of >30%. A rises of current generation were observed every time after the medium was exchanged, which indicates the microbial activity is responsible for current generation and CH 4 production. The maximum CH 4 production rates in 1st, 2nd and 3rd cycle were 108, 179 and 340 mmol m -3 day -1 respectively, which shows a growth of performance in microbial catalytic ability. These results suggest that it is feasible to scale up the EM system and, however, further studies are required to commercialize the system as a CCS technology. [ABSTRACT FROM AUTHOR]

Anaerobic digestion of sewage sludge produces large amounts of CO2 which contribute to global CO2 emissions. Capture and conversion of CO2 into valuable products is a novel way to reduce CO2 emissions and valorize it. Membrane contactors can be used for CO2 capture in liquid media, while bioelectrochemical systems (BES) can valorize dissolved CO2 converting it to CH4, through electromethanogenesis (EMG). At the same time, EMG process, which requires electricity to drive the conversion, can be utilized to store electrical energy (eventually coming from renewables surplus) as methane. The study aims integrating the two technologies at a laboratory scale, using for the first time real wastewater as CO2 capture medium. Five replicate EMG-BES cells were built and operated individually at 0.7 V. They were fed with both synthetic and real wastewater, saturated with CO2 by membrane contactors. In a subsequent experimental step, four EMG-BES cells were electrical stacked in series while one was kept as reference. CH4 production reached 4.6 L CH4 m−2 d−1, in line with available literature data, at a specific energy consumption of 16⁻18 kWh m−3 CH4 (65% energy efficiency). Organic matter was removed from wastewater at approximately 80% efficiency. CO2 conversion efficiency was limited (0.3⁻3.7%), depending on the amount of CO2 injected in wastewater. Even though achieved performances are not yet competitive with other mature methanation technologies, key knowledge was gained on the integrated operation of membrane contactors and EMG-BES cells, setting the base for upscaling and future implementation of the technology.

This paper deals with the design, operation, modeling, and grid integration of bioelectrochemical systems (BES) for power-to-gas application, through an electromethanogenesis process. The paper objective is to show that BES-based power-to-gas energy storage is feasible on a large scale, showing a first approximation that goes from the BES design and operation to the electrical grid integration. It is the first study attempting to cover all aspects of a BES-based power-to-gas technology, on authors’ knowledge. Designed BES reactors were based on a modular architecture, suitable for a future scaling-up. They were operated in steady state for eight months, and continuously monitored in terms of power consumption, water treatment, and biomethane production, in order to obtain data for the following modeling activity. A black box linear model of the BES was computed by using least-square methods, and validated through comparison with collected experimental data. Afterwards, a BES stack was simulated through several series and parallel connections of reactors, in order to obtain higher power consumption and test the grid integration of a real application system. The renewable energy surplus and energy price variability were evaluated for the grid integration of the BES stack. The BES stack was then simulated as energy storage system during low energy price periods, and tested experimentally with a real time system.

• Electromethanogenesis is resilient to power supply interruptions. • Power interruptions with no H 2 supply had a large impact on methanogens. • Power interruptions with no H 2 supply induced large variability. • Power interruptions with H 2 supply limited the metabolism of electrotrophs. • Shifts in microbial populations do not correlate methane production rates. The need to accommodate power fluctuations intrinsic to high-renewable systems will demand in the future the implementation of large quantities of energy storage capacity. Microbial electromethanogenesis (EM) can potentially absorb the excess of renewable energy and store it as CH₄. However, it is still unknown how power fluctuations impact on the performance of EM systems. In this study, power gaps from 24 to 96 h were applied to two 0.5 L EM reactors to assess the effect of power interruptions on current density, methane production and current conversion efficiency. In addition, the cathodes were operated with and without external H₂ supplementation during the power-off periods to analyse how power outages affect the two main metabolic stages of the EM (i.e.: the hydrogenic and methanogenic steps). Methane production rates kept around 1000 mL per m2 of electrode and per day regardless of the duration of the power interruptions and of the supplementation of hydrogen. Interestingly, current density increased in the absence of hydrogen (averaged current density during hydrogen supplementation was 0.36 A·m−2, increasing up to 0.58 A·m−2 without hydrogen). However current was less efficiently used in the production of methane with no hydrogen supplementation. Nevertheless, when the electrical power was restored after the power interruption experiments, performance parameters were similar to those observed before. These results indicate that EM is resilient to power fluctuations, which reinforces the opportunity of using EM as a technology for renewable energy storage. [ABSTRACT FROM AUTHOR]

The use of liquid fraction of pressed municipal solid waste (LPW) for hydrogen production was evaluated via electrohydrogenesis in a single-chamber microbial electrolysis cell (MEC). The highest hydrogen production (0.38 ± 0.09 m 3 m −3 d −1 and 30.94 ± 7.03 mmol g −1 COD added ) was achieved at an applied voltage of 3.0 V and pH 5.5, increasing by 2.17-fold than those done at the same voltage without pH adjustment (pH 7.0). Electrohydrogenesis was accomplished by anodic oxidation of fermentative end-products (i.e. acetate, as well as propionate and butyrate after their acetification), with overall hydrogen recovery of 49.5 ± 11.3% of COD added . These results affirm for the first time that electrohydrogenesis can be a noteworthy alternative for hydrogen recovery from LPW and simultaneous organics removal. Electrohydrogenesis efficiency of this system has potential to improve provided that electron recycling, electromethanogenesis and deposition of non-conductive aggregates on cathode surface, etc. are effectively controlled. [ABSTRACT FROM AUTHOR]