Korneel Rabaey

Microbial fuel cell (MFC) research is a rapidly evolving field that lacks established terminology and methods for the analysis of system performance. This makes it difficult for researchers to compare devices on an equivalent basis. The construction and analysis of MFCs requires knowledge of different scientific and engineering fields, ranging from microbiology and electrochemistry to materials and environmental engineering. Describing MFC systems therefore involves an understanding of these different scientific and engineering principles. In this paper, we provide a review of the different materials and methods used to construct MFCs, techniques used to analyze system performance, and recommendations on what information to include in MFC studies and the most useful ways to present results.

Microbial fuel cells (MFCs) provide new opportunities for the sustainable production of energy from biodegradable, reduced compounds. MFCs function on different carbohydrates but also on complex substrates present in wastewaters. As yet there is limited information available about the energy metabolism and nature of the bacteria using the anode as electron acceptor; few electron transfer mechanisms have been established unequivocally. To optimize and develop energy production by MFCs fully this knowledge is essential. Depending on the operational parameters of the MFC, different metabolic pathways are used by the bacteria. This determines the selection and performance of specific organisms. Here we discuss how bacteria use an anode as an electron acceptor and to what extent they generate electrical output. The MFC technology is evaluated relative to current alternatives for energy generation.

Waste biomass is a cheap and relatively abundant source of electrons for microbes capable of producing electrical current outside the cell. Rapidly developing microbial electrochemical technologies, such as microbial fuel cells, are part of a diverse platform of future sustainable energy and chemical production technologies. We review the key advances that will enable the use of exoelectrogenic microorganisms to generate biofuels, hydrogen gas, methane, and other valuable inorganic and organic chemicals. Moreover, we examine the key challenges for implementing these systems and compare them to similar renewable energy technologies. Although commercial development is already underway in several different applications, ranging from wastewater treatment to industrial chemical production, further research is needed regarding efficiency, scalability, system lifetimes, and reliability.

Microbial fuel cells hold great promise as a sustainable biotechnological solution to future energy needs. Current efforts to improve the efficiency of such fuel cells are limited by the lack of knowledge about the microbial ecology of these systems. The purposes of this study were (i) to elucidate whether a bacterial community, either suspended or attached to an electrode, can evolve in a microbial fuel cell to bring about higher power output, and (ii) to identify species responsible for the electricity generation. Enrichment by repeated transfer of a bacterial consortium harvested from the anode compartment of a biofuel cell in which glucose was used increased the output from an initial level of 0.6 W m(-2) of electrode surface to a maximal level of 4.31 W m(-2) (664 mV, 30.9 mA) when plain graphite electrodes were used. This result was obtained with an average loading rate of 1 g of glucose liter(-1) day(-1) and corresponded to 81% efficiency for electron transfer from glucose to electricity. Cyclic voltammetry indicated that the enhanced microbial consortium had either membrane-bound or excreted redox components that were not initially detected in the community. Dominant species of the enhanced culture were identified by denaturing gradient gel electrophoresis and culturing. The community consisted mainly of facultative anaerobic bacteria, such as Alcaligenes faecalis and Enterococcus gallinarum, which are capable of hydrogen production. Pseudomonas aeruginosa and other Pseudomonas species were also isolated. For several isolates, electrochemical activity was mainly due to excreted redox mediators, and one of these mediators, pyocyanin produced by P. aeruginosa, could be characterized. Overall, the enrichment procedure, irrespective of whether only attached or suspended bacteria were examined, selected for organisms capable of mediating the electron transfer either by direct bacterial transfer or by excretion of redox components.

Bioelectrochemical systems (BESs), such as microbial fuel cells (MFCs) and microbial electrolysis cells (MECs), are generally regarded as a promising future technology for the production of energy from organic material present in wastewaters. The current densities that can be generated with laboratory BESs now approach levels that come close to the requirements for practical applications. However, full-scale implementation of bioelectrochemical wastewater treatment is not straightforward because certain microbiological, technological and economic challenges need to be resolved that have not previously been encountered in any other wastewater treatment system. Here, we identify these challenges, provide an overview of their implications for the feasibility of bioelectrochemical wastewater treatment and explore the opportunities for future BESs.

High-rate electron transfer toward an anode in microbial fuel cells (MFCs) has thus far not been described for bacteria-producing soluble redox mediators. To studythe mechanism of electron transfer, we used a MFC isolate, Pseudomonas aeruginosa strain KRP1. Bacterial electron transfer toward the MFC anode was enabled through pyocyanin and phenazine-1-carboxamide. The presence of the anode stimulated pyocyanin production. Mutant strains, deficient in the synthesis of pyocyanin and phenazine-1-carboxamide, were unable to achieve substantial electron transfer and reached only 5% of the wild type's power output. Upon pyocyanin addition, the power output was restored to 50%. Pyocyanin was not only used by P. aeruginosa to improve electron transfer but as well enhanced electron transfer by other bacterial species. The finding that one bacterium can produce electron shuttles, which can be used also by other bacteria, to enhance electron-transfer rate and growth, has not been shown before. These findings have considerable implications with respect to the power output attainable in MFCs.

Connecting several microbial fuel cell (MFC) units in series or parallel can increase voltage and current; the effect on the microbial electricity generation was as yet unknown. Six individual continuous MFC units in a stacked configuration produced a maximum hourly averaged power output of 258 W m(-3) using a hexacyanoferrate cathode. The connection of the 6 MFC units in series and parallel enabled an increase of the voltages (2.02 V at 228 W m(-3)) and the currents (255 mA at 248 W m(-3)), while retaining high power outputs. During the connection in series, the individual MFC voltages diverged due to microbial limitations at increasing currents. With time, the initial microbial community decreased in diversity and Gram-positive species became dominant. The shift of the microbial community accompanied a tripling of the short time power output of the individual MFCs from 73 W m(-3) to 275 W m(-3), a decrease of the mass transfer limitations and a lowering of the MFC internal resistance from 6.5 +/- 1.0 to 3.9 +/- 0.5 omega. This study demonstrates a clear relation between the electrochemical performance and the microbial composition of MFCs and further substantiates the potential to generate useful energy by means of MFCs.

Microbial fuel cells (MFCs) that remove carbon as well as nitrogen compounds out of wastewater are of special interest for practice. We developed a MFC in which microorganisms in the cathode performed a complete denitrification by using electrons supplied by microorganisms oxidizing acetate in the anode. The MFC with a cation exchange membrane was designed as a tubular reactor with an internal cathode and was able to remove up to 0.146 kg NO(3-)-N m(-3) net cathodic compartment (NCC) d(-1) (0.080 kg NO(3-)-N m(-3) total cathodic compartment d(-1) (TCC)) at a current of 58 A m(-3) NCC (32 A m(-3) TCC) and a cell voltage of 0.075 V. The highest power output in the denitrification system was 8 W m(-3) NCC (4 W m(-3) TCC) with a cell voltage of 0.214 V and a current of 35 A m(-3) NCC. The denitrification rate and the power production was limited bythe cathodic microorganisms, which only denitrified significantly at a cathodic electrode potential below 0 V versus standard hydrogen electrode (SHE). This is, to our knowledge, the first study in which a MFC has both a biological anode and cathode performing simultaneous removal of an organic substrate, power production, and complete denitrification without relying on H2-formation or external added power.

A tubular, single-chambered, continuous microbial fuel cell (MFC) that generates high power outputs using a granular graphite matrix as the anode and a ferricyanide solution as the cathode is described. The maximal power outputs obtained were 90 and 66 W m(-3) net anodic compartment (NAC) (48 and 38 W m(-3) total anodic compartment (TAC)) for feed streams based on acetate and glucose, respectively, and 59 and 48 W m(-3) NAC for digester effluent and domestic wastewater, respectively. For acetate and glucose, the total Coulombic conversion efficiencies were 75 +/- 5% and 59 +/- 4%, respectively, at loading rates of 1.1 kg chemical oxygen demand m(-3) NAC volume day(-1). When wastewater was used, of the organic matter effectively removed (i.e., 22% at a loading of 2 kg organic matter m(-3) NAC day(-1)), up to 96% was converted to electricity on a Coulombic basis. The lower overall efficiency of the wastewater-treating reactors is related to the presence of nonreadily biodegradable organics and the interference of alternative electron acceptors such as sulfate present in the wastewater. To further improve MFCs, focus has to be placed on the enhanced conversion of nonrapidly biodegradable material and the better directing of the anode flow toward the electrode instead of to alternative electron acceptors. Also the use of sustainable, open-air cathodes is a critical issue for practical implementation.

Phosphorus (P) is an essential element for all life on earth. However, natural P resources (phosphate rock) are depleting. The authors describe the current situation and a forecast for future phosphate production and reserves. The current depletion of phosphate reserves and the increasingly stringent discharge regulations have led to the development of various P-recovery techniques from wastewater. Existing full-scale P-recovery techniques from the liquid phase, sludge phase, and sludge ash are reviewed. Although the full-scale P-recovery techniques have been shown to be technologically feasible, the economical feasibility, legislation and national policies are the major reasons why these techniques are not yet operational worldwide.

Bio-electrochemical systems (BESs) have recently emerged as an exciting technology. In a BES, bacteria interact with electrodes using electrons, which are either removed or supplied through an electrical circuit. The most-described type of BES is microbial fuel cells (MFCs), in which useful power is generated from electron donors as, for example, present in wastewater. This form of charge transport, known as extracellular electron transfer, was previously extensively described with respect to metals such as iron and manganese. The importance of these interactions in global biogeochemical cycles is essentially undisputed. A wide variety of bacteria can participate in extracellular electron transfer, and this phenomenon is far more widespread than previously thought. The use of BESs in diverse research projects is helping elucidate the mechanism by which bacteria shuttle electrons externally. New forms of interactions between bacteria have been discovered demonstrating how multiple populations within microbial communities can co-operate to achieve energy generation. New environmental processes that were difficult to observe or study previously can now be simulated and improved via BESs. Whereas pure culture studies make up the majority of the studies performed thus far, even greater contributions of BESs are expected to occur in natural environments and with mixed microbial communities. Owing to their versatility, unmatched level of control and capacity to sustain novel processes, BESs might well serve as the foundation of a new environmental biotechnology. While highlighting some of the major breakthroughs and addressing only recently obtained data, this review points out that despite rapid progress, many questions remain unanswered.

The recent demonstration of cathodic nitrate reduction in a microbial fuel cell (MFC) creates opportunities for a new technology for nitrogen removal from wastewater. A novel process configuration that achieves both carbon and nitrogen removal using MFC is designed and demonstrated. The process involves feeding the ammonium-containing effluent from the carbon-utilising anode to an external biofilm-based aerobic reactor for nitrification, and then feeding the nitrified liquor to the MFC cathode for nitrate reduction. Removal rates up to 2 kg COD m−3 NCC d−1 (chemical oxygen demand: COD, net cathodic compartment: NCC) and 0.41 kg NO3−-N m−3 NCC d−1 were continuously achieved in the anodic and cathodic compartment, respectively, while the MFC was producing a maximum power output of 34.6±1.1 W m−3 NCC and a maximum current of 133.3±1.0 A m−3 NCC. In comparison to conventional activated sludge systems, this MFC-based process achieves nitrogen removal with a decreased carbon requirement. A COD/N ratio of approximately 4.5 g COD g−1 N was achieved, compared to the conventionally required ratio of above 7. We have demonstrated that also nitrite can be used as cathodic electron acceptor. Hence, upon creating a loop concept based on nitrite, a further reduction of the COD/N ratio would be possible. The process is also more energy effective not only due to the energy production coupled with denitrification, but also because of the reduced aeration costs due to minimised aerobic consumption of organic carbon.

The reduction of oxygen at the cathode is one of the major bottlenecks of microbial fuel cells (MFCs). While research so far has mainly focused on chemical catalysis of this oxygen reduction, here we present a continuously wetted cathode with microorganisms that act as biocatalysts for oxygen reduction. We combined the anode of an acetate oxidizing tubular microbial fuel cell with an open air biocathode for electricity production. The maximum power production was 83 +/- 11 W m(-3) MFC (0.183 L MFC) for batch-fed systems (20-40% Coulombic yield) and 65 +/- 5 W m(-3) MFC for a continuous system with an acetate loading rate of 1.5 kg COD m(-3) day(-1) (90 +/- 3% Coulombic yield). Electrochemical precipitation of manganese oxides on the cathodic graphite felt decreased the start-up period with approximately 30% versus a non-treated graphite felt. After the start-up period, the cell performance was similar for the pretreated and non-treated cathodic electrodes. Several reactor designs were tested, and it was found that enlargement of the 0.183 L MFC reactor by a factor 2.9-3.8 reduced the volumetric power output by 60-67%. Biocathodes alleviate the need to use noble or non-noble catalysts for the reduction of oxygen, which increases substantially the viability and sustainability of MFCs.

Hydrogen peroxide (H2O2) is an important industrial chemical, but its current production methods are highly energy-intensive. This study presents a novel process for the production of H2O2 based on the bioelectrochemical oxidation of wastewater organics at an anode coupled to the cathodic reduction of oxygen to H2O2. At an applied voltage of 0.5 V, this system was capable of producing ∼1.9 ± 0.2 kg H2O2/m3/day from acetate at an overall efficiency of 83.1 ± 4.8%. As most of the required energy was derived from the acetate, the system had a low energy requirement of ∼0.93 kWh/kg H2O2.

Abstract Conventional anaerobic digestion based bioconversion processes produce biogas and have as such been widely applied for the production of renewable energy so far. An innovative technology, based on the use of microbial fuel cells, is considered as a new pathway for bioconversion processes towards electricity. In comparison with conventional anaerobic digestion, the microbial fuel cell technology holds some specific advantages, such as its applicability for the treatment of low concentration substrates at temperatures below 20 °C, where anaerobic digestion generally fails to function. This provides some specific application niches of the microbial fuel cell technology where it does not compete with but complements the anaerobic digestion technology. However, microbial fuel cells still face important limitations in terms of large‐scale application. The limitations involve the investment costs, upscale technical issues and the factors limiting the performance, both in terms of anodic and cathodic electron transfer. Research to render the microbial fuel cell technology more economically feasible and applicable should focus on reactor configuration, power density and the material costs.

Thus far, microbial fuel cells (MFCs) have been used to convert carbon-based substrates to electricity. However, sulfur compounds are ubiquitously present in organic waste and wastewater. In this study, a MFC with a hexacyanoferrate cathodic electrolyte was used to convert dissolved sulfide to elemental sulfur. Two types of MFCs were used, a square type closed to the air and a tubular type in which the cathode compartment was open to the air. The square-type MFCs demonstrated a potential-dependent conversion of sulfide to sulfur. In the tubular system, up to 514 mg sulfide L(-1) net anodic compartment (NAC) day(-1) (241 mg L(-1) day(-1) total anodic compartment, TAC) was removed. The sulfide oxidation in the anodic compartment resulted in electricity generation with power outputs up to 101 mW L(-1) NAC (47 W m(-3) TAC). Microbial fuel cells were coupled to an anaerobic upflow anaerobic sludge blanket reactor, providing total removals of up to 98% and 46% of the sulfide and acetate, respectively. The MFCs were capable of simultaneously removing sulfate via sulfide. This demonstrates that digester effluents can be polished by a MFC for both residual carbon and sulfur compounds. The recovery of electrons from sulfides implies a recovery of energy otherwise lost in the methane digester.

Microbial fuel cells (MFCs) can use nitrate as a cathodic electron acceptor, allowing for simultaneous removal of carbon (at the anode) and nitrogen (at the cathode). In this study, we supplemented the cathodic process with in situ nitrification through specific aeration, and thus obtained simultaneous nitrification and denitrification (SND) in the one half-cell. Synthetic wastewater containing acetate and ammonium was supplied to the anode; the effluent was subsequently directed to the cathode. The influence of oxygen levels and carbon/nitrogen concentrations and ratios on the system performances was investigated. Denitrification occurred simultaneously with nitrification at the cathode, producing an effluent with levels of nitrate and ammonium as low as 1.0+/-0.5 mg N L(-1) and 2.13+/-0.05 mg N L(-1), respectively, resulting in a nitrogen removal efficiency of 94.1+/-0.9%. The integration of the nitrification process into the cathode solves the drawback of ammonium losses due to diffusion between compartments in the MFC, as previously reported in a system operating with external nitrification stage. This work represents the first successful attempt to combine SND and organics oxidation while producing electricity in an MFC.

Different microbial pathways can elongate the carbon chains of molecules in open cultures of microbial populations (i.e.reactor microbiomes) under anaerobic conditions.Here, we discuss three such pathways: 1. homoacetogenesis to combine two carbon dioxide molecules into acetate; 2. succinate formation to elongate glycerol with one carbon from carbon dioxide; and 3. reverse b oxidation to elongate short-chain carboxylates with two carbons into medium-chain carboxylates, leading to more energy-dense and insoluble products (e.g.easier to separate from solution).The ability to use reactor microbiomes to treat complex substrates can simultaneously address two pressing issues: 1. providing proper waste management; and 2. producing renewable chemicals and fuels.

Azo dyes are ubiquitously used in the textile industry. These dyes need to be removed from the effluent prior to discharge to sewage due to their intense color and toxicity. In this study we investigated the use of a bioelectrochemical system (BES) to abioticlly cathodic decolorization of a model azo dye, Acid Orange 7 (AO7), where the process was driven by microbial oxidation of acetate at the anode. Effective decolorization of AO7 at rates up to 2.64 ± 0.03 mol m−3 NCC d−1 (net cathodic compartment, NCC) was achieved at the cathode, with concomitant energy recovery. The AO7 decolorization rate was significantly enhanced when the BES was supplied with power, reaching 13.18 ± 0.05 mol m−3 NCC d−1 at an energy consumption 0.012 ± 0.001 kWh mol−1 AO7 (at a controlled cathode potential of −400 mV vs SHE). Compared with conventional anaerobic biological methods, the required dosage of organic cosubstrate was significantly reduced in the BES. A possible cathodic reaction mechanism for the decolorization of AO7 is suggested based on the decolorization products identified: the azo bond of AO7 was cleaved at the cathode, resulting in the formation of the colorless sulfanilic acid and 1-amino-2-naphthol.

Abstract A replicate long-term experiment was conducted using anaerobic digestion (AD) as a model process to determine the relative role of niche and neutral theory on microbial community assembly, and to link community dynamics to system performance. AD is performed by a complex network of microorganisms and process stability relies entirely on the synergistic interactions between populations belonging to different functional guilds. In this study, three independent replicate anaerobic digesters were seeded with the same diverse inoculum, supplied with a model substrate, α-cellulose, and operated for 362 days at a 10-day hydraulic residence time under mesophilic conditions. Selective pressure imposed by the operational conditions and model substrate caused large reproducible changes in community composition including an overall decrease in richness in the first month of operation, followed by synchronised population dynamics that correlated with changes in reactor performance. This included the synchronised emergence and decline of distinct Ruminococcus phylotypes at day 148, and emergence of a Clostridium and Methanosaeta phylotype at day 178, when performance became stable in all reactors. These data suggest that many dynamic functional niches are predictably filled by phylogenetically coherent populations over long time scales. Neutral theory would predict that a complex community with a high degree of recognised functional redundancy would lead to stochastic changes in populations and community divergence over time. We conclude that deterministic processes may play a larger role in microbial community dynamics than currently appreciated, and under controlled conditions it may be possible to reliably predict community structural and functional changes over time.

The focus of this study was to investigate the effects of surface charge and surface hydrophobicity on anodic biofilm formation, biofilm community composition, and current generation in bioelectrochemical systems (BESs). Glassy carbon surfaces were modified with −OH, −CH3, −SO3–, or −N+(CH3)3 functional groups by electrochemical reduction of aryl diazonium salts and then used as anodes with poised potential of −0.2 V (vs Ag/AgCl). The average startup times and final current densities for the −N+(CH3)3, −OH, −SO3–, and −CH3, electrodes were (23 d, 0.204 mA/cm2), (25.4 d, 0.149 mA/cm2), (25.9 d, 0.114 mA/cm2), and (37.2 d, 0.048 mA/cm2), respectively. Biofilms on different surfaces were analyzed by nonturnover cyclic voltammetry (CV), fluorescence in situ hybridization (FISH), and 16S rRNA gene amplicon pyrosequencing. The results demonstrated that 1) differences in the maximum current output between surface modifications was correlated with biomass quantity, and 2) all biofilms were dominated by Geobacter populations, but the composition of −CH3-associated biofilms differed from those formed on surfaces with different chemical modification. This study shows that anode surface charge and hydrophobicity influences biofilm development and can lead to significant differences in BESs performance. Positively charged and hydrophilic surfaces were more selective to electroactive microbes (e.g. Geobacter) and more conducive for electroactive biofilm formation.

Living plants transport substantial amounts of organic material into the soil.This process, called rhizodeposition, provides the substrate for the rhizospheric microbial community.In this study, a laboratory-scale sediment microbial fuel cell, of which the anode is positioned in the rhizosphere of the rice plants, is used to microbially oxidize the plant-derived organics.An electrical current was generated through the in situ oxidation of rhizodeposits from living rice plants.The electrical power output of a sediment microbial fuel cell was found to be a factor 7 higher in the presence of actively growing plants.This process offers the potential of light-driven power generation from living plants in a nondestructive way.Sustainable power productions up to 330 W ha -1 could be attributed to the oxidation of the plant-derived compounds.

Microbial fuel cells (MFCs) have the potential to combine wastewater treatment efficiency with energetic efficiency. One of the major impediments to MFC implementation is the operation of the cathode compartment, as it employs environmentally unfriendly catalysts such as platinum. As recently shown, bacteria can facilitate sustainable and cost-effective cathode catalysis for nitrate and also oxygen. Here we describe a carbon cathode open to the air, on which attached bacteria catalyzed oxygen reduction. The bacteria present were able to reduce oxygen as the ultimate electron acceptor using electrons provided by the solid-phase cathode. Current densities of up to 2.2 A m(-2) cathode projected surface were obtained (0.303+/-0.017 W m(-2), 15 W m(-3) total reactor volume). The cathodic microbial community was dominated by Sphingobacterium, Acinetobacter and Acidovorax sp., according to 16S rRNA gene clone library analysis. Isolates of Sphingobacterium sp. and Acinetobacter sp. were obtained using H(2)/O(2) mixtures. Some of the pure culture isolates obtained from the cathode showed an increase in the power output of up to three-fold compared to a non-inoculated control, that is, from 0.015+/-0.001 to 0.049+/-0.025 W m(-2) cathode projected surface. The strong decrease in activation losses indicates that bacteria function as true catalysts for oxygen reduction. Owing to the high overpotential for non-catalyzed reduction, oxygen is only to a limited extent competitive toward the electron donor, that is, the cathode. Further research to refine the operational parameters and increase the current density by modifying the electrode surface and elucidating the bacterial metabolism is warranted.

Nitrobenzene (NB) is a toxic compound that is often found as a pollutant in the environment. The present removal strategies suffer from high cost or slow conversion rate. Here, we investigated the conversion of NB to aniline (AN), a less toxic endproduct that can easily be mineralized, using a fed-batch bioelectrochemical system with microbially catalyzed cathode. When a voltage of 0.5 V was applied in the presence of glucose, 88.2 ± 0.60% of the supplied NB (0.5 mM) was transformed to AN within 24 h, which was 10.25 and 2.90 times higher than an abiotic cathode and open circuit controlled experiment, respectively. AN was the only product detected during bioelectrochemical reduction of NB (maximum efficiency 98.70 ± 0.87%), whereas in abiotic conditions nitrosobenzene was observed as intermediate of NB reduction to AN (decreased efficiency to 73.75 ± 3.2%). When glucose was replaced by NaHCO(3), the rate of NB degradation decreased about 10%, selective transformation of NB to AN was still achieved (98.93 ± 0.77%). Upon autoclaving the cathode electrode, nitrosobenzene was formed as an intermediate, leading to a decreased AN formation efficiency of 71.6%. Cyclic voltammetry highlighted higher peak currents as well as decreased overpotentials for NB reduction at the biocathode. 16S rRNA based analysis of the biofilm on the cathode indicated that the cathode was dominated by an Enterococcus species closely related to Enterococcus aquimarinus.

Oxygen is the most sustainable electron acceptor currently available for microbial fuel cell (MFC) cathodes. However, its high overpotential for reduction to water limits the current that can be produced. Several materials and catalysts have previously been investigated in order to facilitate oxygen reduction at the cathode surface. This study shows that significant stable currents can be delivered by using a non-catalyzed cathode made of granular graphite. Power outputs up to 21 W m−3 (cathode total volume) or 50 W m−3 (cathode liquid volume) were attained in a continuous MFC fed with acetate. These values are higher than those obtained in several other studies using catalyzed graphite in various forms. The presence of nanoscale pores on granular graphite provides a high surface area for oxygen reduction. The current generated with this cathode can sustain an anodic volume specific COD removal rate of 1.46 kgCOD m−3 d−1, which is higher than that of a conventional aerobic process. This study demonstrates that microbial fuel cells can be operated efficiently using high surface graphite as cathode material. This implies that research on microbial fuel cell cathodes should not only focus on catalysts, but also on high surface area materials.

Existing wastewater treatment options are generally perceived as energy intensive and environmentally unfriendly. Much attention has been focused on two new approaches in the past years, (i) microbial fuel cells and (ii) microbial electrolysis cells, which directly generate electrical current or chemical products, respectively, during wastewater treatment. These systems are commonly denominated as bioelectrochemical systems, and a multitude of claims have been made in the past regarding the environmental impact of these treatment options. However, an in-depth study backing these claims has not been performed. Here, we have conducted a life cycle assessment (LCA) to compare the environmental impact of three industrial wastewater treatment options, (i) anaerobic treatment with biogas generation, (ii) a microbial fuel cell treatment, with direct electricity generation, and (iii) a microbial electrolysis cell, with hydrogen peroxide production. Our analysis showed that a microbial fuel cell does not provide a significant environmental benefit relative to the “conventional” anaerobic treatment option. However, a microbial electrolysis cell provides significant environmental benefits through the displacement of chemical production by conventional means. Provided that the target conversion level of 1000 A·m−3 can be met, the decrease in greenhouse gas emissions and other environmentally harmful emissions (e.g., aromatic hydrocarbons) of the microbial electrolysis cell will be a key driver for the development of an industrial standard for this technology. Evidently, this assessment is highly dependent on the underlying assumptions, such as the used reactor materials and target performance. This provides a challenge and an opportunity for researchers in the field to select and develop appropriate and environmentally benign materials of construction, as well as demonstrate the required 1000 A·m−3 performance at pilot and full scale.

Microbial electrocatalysis refers to the use of microorganisms to catalyze electrode reactions. Many processes have been developed on this principle, ranging from power generation to CO2 conversion using bioelectrochemical systems. The nature of the interface between the microorganisms and the electrodes determines the functioning and efficiency of these systems. This interface can be manipulated in terms of chemical and topographical features to better understand the interaction at nanometer and micrometer scales. Here we discuss how the electrode surface topography and chemistry impact the microorganism–electrode interaction both for direct and indirect electron transfer mechanisms. It appears that composite materials that combine high conductivity with excellent biocompatibility are most attractive towards application. In most cases this implies a combination of a metallic backbone with a carbon coating with a defined topography and chemistry.

The advent of renewable energy conversion systems exacerbates the existing issue of intermittent excess power. Microbial electrosynthesis can use this power to capture CO2 and produce multicarbon compounds as a form of energy storage. As catalysts, microbial populations can be used, provided side reactions such as methanogenesis are avoided. Here a simple but effective approach is presented based on enrichment of a robust microbial community via several culture transfers with H2:CO2 conditions. This culture produced acetate at a concentration of 1.29 ± 0.15 g L(-1) (maximum up to 1.5 g L(-1); 25 mM) from CO2 at a fixed current of -5 Am(-2) in fed-batch bioelectrochemical reactors at high N2:CO2 flow rates. Continuous supply of reducing equivalents enabled acetate production at a rate of 19 ± 2 gm(-2)d(-1) (projected cathode area) in several independent experiments. This is a considerably high rate compared with other unmodified carbon-based cathodes. 58 ± 5% of the electrons was recovered in acetate, whereas 30 ± 10% of the electrons was recovered in H2 as a secondary product. The bioproduction was most likely H2 based; however, electrochemical, confocal microscopy, and community analyses of the cathodes suggested the possible involvement of the cathodic biofilm. Together, the enrichment approach and galvanostatic operation enabled instant start-up of the electrosynthesis process and reproducible acetate production profiles.

Microbial electrosynthesis (MES) is an electrochemical process used to drive microbial metabolism for bio-production, such as the reduction of CO2 into industrially relevant organic products as an alternative to current fossil-fuel-derived commodities. After a decade of research on MES from CO2, figures of merit have increased significantly but are plateauing yet far from those expected to allow competitiveness for synthesis of commodity chemicals. Here we discuss the substantial technological shortcomings still associated with MES and evoke possible ways to mitigate them. It appears particularly challenging to obtain both relevant production rates (driven by high current densities) and energy conversion efficiency (i.e. low cell voltage) in microbial-compatible electrolytes. More competitive processes could arise by decoupling effective abiotic electroreductions (e.g. CO2 to CO or ethanol; H2 evolution) with subsequent fermentation processes.

Electro-fermentation (EF) merges traditional industrial fermentation with electrochemistry. An imposed electrical field influences the fermentation environment and microbial metabolism in either a reductive or oxidative manner. The benefit of this approach is to produce target biochemicals with improved selectivity, increase carbon efficiency, limit the use of additives for redox balance or pH control, enhance microbial growth, or in some cases enhance product recovery. We discuss the principles of electrically driven fermentations and how EF can be used to steer both pure culture and microbiota-based fermentations. An overview is given on which advantages EF may bring to both existing and innovative industrial fermentation processes, and which doors might be opened in waste biomass utilization towards added-value biorefineries.

The production of biofuels and biochemicals is highly electron intensive. To divert fermentative and respiratory pathways to the product of interest, additional electrons (i.e. reducing power) are often needed. Meanwhile, the past decade has seen the breakthrough of sustainable electricity sources such as solar and wind. Microbial electrosynthesis (MES) is at the nexus of both, as it uses electrical energy as source of reducing power for microorganisms. This review addresses the key opportunities and challenges for MES. While exciting as a concept, MES needs to overcome many biological, electrochemical, logistical and economic challenges. Particularly the latter is critical, as on a ‘per electron basis’ MES does not yet appear to deliver a substantial benefit relative to existing approaches.

Ammonia inhibition during anaerobic digestion limits the substrate loading rate and endangers process stability. Furthermore, digestates are interesting feedstocks for nutrient recovery. In this lab-scale study, an electrochemical cell was used to investigate the NH4+ flux from anode to cathode. Under optimal conditions with synthetic wastewater, an NH4+ charge transfer efficiency of 96% and NH4+ flux of 120 g N m–2 d–1 could be obtained at a concomitant electricity input of 5 kWh kg–1 N removed. A more selective NH4+ transfer could be established by maintaining a high concentration of other cations in the cathode compartment. Comparable NH4+ fluxes could be obtained with digestate at an electrical power input of 13 kWh kg–1 N removed and 41% current efficiency. The ammonium level in the digestate could be lowered from 2.1 to 0.8 – 1.2 g N L–1. Interestingly, also potassium fluxes of up to 241 g K+ m–2 d–1 could be obtained at 23% current efficiency. As the cathode can be operated at high pH without the need for chemical addition, stripping and absorption of dissolved ammonia could reach 100% efficiency. By valorization of the generated side products, this technology shows economic potential for practical application.

Microbial electrosynthesis (MES) is a process that uses electricity as an energy source for driving the production of chemicals and fuels using microorganisms and CO2 or organics as carbon sources. The development of this highly interdisciplinary technology on the interface between biotechnology and electrochemistry requires knowledge and expertise in a variety of scientific and technical areas. The rational development and commercialization of MES can be achieved at a faster pace if the research data and findings are reported in appropriate and uniformly accepted ways. Here we provide a framework for reporting on MES research and propose several pivotal performance indicators to describe these processes. Linked to this study is an online tool to perform necessary calculations and identify data gaps. A key consideration is the calculation of effective energy expenditure per unit product in a manner enabling cross comparison of studies irrespective of reactor design. We anticipate that the information provided here on different aspects of MES ranging from reactor and process parameters to chemical, electrochemical, and microbial functionality indicators will assist researchers in data presentation and ease data interpretation. Furthermore, a discussion on secondary MES aspects such as downstream processing, process economics and life cycle analysis is included.

Excessive CO2 emissions in the atmosphere from anthropogenic activity can be divided into point sources and diffuse sources. The capture of CO2 from flue gases of large industrial installations and its conversion into fuels and chemicals with fast catalytic processes seems technically possible. Some emerging technologies are already being demonstrated on an industrial scale. Others are still being tested on a laboratory or pilot scale. These emerging chemical technologies can be implemented in a time window ranging from 5 to 20 years. The massive amounts of energy needed for capturing processes and the conversion of CO2 should come from low-carbon energy sources, such as tidal, geothermal, and nuclear energy, but also, mainly, from the sun. Synthetic methane gas that can be formed from CO2 and hydrogen gas is an attractive renewable energy carrier with an existing distribution system. Methanol offers advantages as a liquid fuel and is also a building block for the chemical industry. CO2 emissions from diffuse sources is a difficult problem to solve, particularly for CO2 emissions from road, water, and air transport, but steady progress in the development of technology for capturing CO2 from air is being made. It is impossible to ban carbon from the entire energy supply of mankind with the current technological knowledge, but a transition to a mixed carbon-hydrogen economy can reduce net CO2 emissions and ultimately lead to a CO2 -neutral world.

Using carbon dioxide for bioproduction combines decreased greenhouse gas emissions with a decreased dependence on fossil carbon for production of multicarbon products. Microbial electrosynthesis (MES) enables this, using renewable energy to drive the reduction of CO2 at the cathode of an electrochemical cell. To date, low product concentrations preclude cost-effective extraction during MES. Here we present an approach that couples production and recovery of acetate in a single, three-chamber reactor system. Acetate was produced at 61% Coulombic efficiency and fully recovered as an acidified stream containing up to 13.5 g L–1 (225 mM) acetic acid, the highest obtained thus far. In contrast to previous MES studies, a single separated acidic product was generated through in situ membrane electrolysis enabling further upgrading.

Throughout the 20th century, the prevailing approach toward nitrogen management in municipal wastewater treatment was to remove ammonium by transforming it into dinitrogen (N2) using biological processes such as conventional activated sludge. While this has been a very successful strategy for safeguarding human health and protecting aquatic ecosystems, the conversion of ammonium into its elemental form is incompatible with the developing circular economy of the 21st century. Equally important, the activated sludge process and other emerging ammonium removal pathways have several environmental and technological limitations. Here, we assess that the theoretical energy embedded in ammonium in domestic wastewater represents roughly 38–48% of the embedded chemical energy available in the whole of the discharged bodily waste. The current routes for ammonium removal not only neglect the energy embedded in ammonium, but they can also produce N2O, a very strong greenhouse gas, with such emissions comprising the equivalent of 14–26% of the overall carbon footprint of wastewater treatment plants. N2O emissions often exceed the carbon emissions related to the electricity consumption for the process requirements of WWTPs. Considering these limitations, there is a need to develop alternative ammonium management approaches that center around recovery of ammonium from domestic wastewater rather than deal with its “destruction” into elemental dinitrogen. Current ammonium recovery techniques are applicable only at orders of magnitude above domestic wastewater strength, and so new techniques based on physicochemical adsorption are of particular interest. A new pathway is proposed that allows for mainstream ammonium recovery from wastewater based on physicochemical adsorption through development of polymer-based adsorbents. Provided adequate adsorbents corresponding to characteristics outlined in this paper are designed and brought to industrial production, this adsorption-based approach opens perspectives for mainstream continuous adsorption coupled with side-stream recovery of ammonium with minimal chemical requirements. This proposed pathway can bring forward an effective resource-oriented approach to upgrade the fate of ammonium in urban water management without generating hidden externalized environmental costs.

One of the main challenges for the 21st century is to balance the increasing demand for high-quality proteins while mitigating environmental impacts. In particular, cropland-based production of protein-rich animal feed for livestock rearing results in large-scale agricultural land-expansion, nitrogen pollution, and greenhouse gas emissions. Here we propose and analyze the long-term potential of alternative animal feed supply routes based on industrial production of microbial proteins (MP). Our analysis reveals that by 2050, MP can replace, depending on socio-economic development and MP production pathways, between 10-19% of conventional crop-based animal feed protein demand. As a result, global cropland area, global nitrogen losses from croplands and agricultural greenhouse gas emissions can be decreased by 6% (0-13%), 8% (-3-8%), and 7% (-6-9%), respectively. Interestingly, the technology to industrially produce MP at competitive costs is directly accessible for implementation and has the potential to cause a major structural change in the agro-food system.

In view of today’s challenges in clean water depletion and wastewater management, electrochemical water treatment processes are increasingly applied for e.g. desalination of brackish water, recovery of resources and energy production from waste streams, and disinfection of wastewater. These electrochemical processes typically make use of an ion-exchange membrane in between the anode and cathode. The choice of material for this membrane is crucial for the performance of the cell and often its performance is the key bottleneck. Over the last decade, research has been focused on the production of ion-exchange nanofibers as membrane material due to their outstanding ionic properties as a result of their specific morphology. Nanofiber membranes are known to have a large specific surface area, flexibility, high porosity and interconnected pores. Different strategies are applied for the production and structural design of these ion-exchange nanofiber membranes, which are discussed in this review. Nanofibers with an ion-exchange functionality can be produced by either pre- or post-functionalization methods, combined with electrospinning. Depending on the application, these nanofiber mats can be used as such, or further membrane processing is possible to improve the dimensional stability, typically by adding a pore-filling matrix in between the nanofibers. Eventually, the current state of research on ion-exchange nanofibers in electrochemical separation and degradation applications is discussed. The many examples highlighted in this review prove the potential of nanofibers as ion-exchangers and provide insights for future research in this area.

Sustainable water management is essential to guaranteeing access to safe water and addressing the challenges posed by climate change, urbanization, and population growth. In a typical household, greywater, which includes everything but toilet waste, constitutes 50-80% of daily wastewater generation and is characterized by low organic strength and high volume. This can be an issue for large urban wastewater treatment plants designed for high-strength operations. Segregation of greywater at the source for decentralized wastewater treatment is therefore necessary for its proper management using separate treatment strategies. Greywater reuse may thus lead to increased resilience and adaptability of local water systems, reduction in transport costs, and achievement of fit-for-purpose reuse. After covering greywater characteristics, we present an overview of existing and upcoming technologies for greywater treatment. Biological treatment technologies, such as nature-based technologies, biofilm technologies, and membrane bioreactors (MBR), conjugate with physicochemical treatment methods, such as membrane filtration, sorption and ion exchange technologies, and ultraviolet (UV) disinfection, may be able to produce treated water within the allowable parameters for reuse. We also provide a novel way to tackle challenges like the demographic variance of greywater quality, lack of a legal framework for greywater management, monitoring and control systems, and the consumer perspective on greywater reuse. Finally, benefits, such as the potential water and energy savings and sustainable future of greywater reuse in an urban context, are discussed.

Microbial fuel cells (MFCs) are emerging as promising technology for the treatment of wastewaters. The potential energy conversion efficiencies are examined. The rates of energy recovery (W/m3 reactor) are reviewed and evaluated. Some recent data relating to potato-processing wastewaters and a hospital wastewater effluent are reported. Finally, a set of process configurations in which MFCs could be useful to treat wastewaters is schematized. Overall, the MFC technology still faces major challenges, particularly in terms of chemical oxygen demand (COD) removal efficiency.

Microbial fuel cells (MFCs) are emerging as a novel technology with a great potential to reduce the costs of wastewater treatment. Their most studied application is organic carbon removal. One of the parameters commonly used to quantify the performance of these cells is the Coulombic efficiency, i.e., the electron recovery as electricity from the removed substrate. However, the "inefficiencies" of the process have never been fully identified. This study presents a method that uses the combination of electrochemical monitoring, chemical analysis, and a titration and off-gas analysis (TOGA) sensor to identify and quantify the sources of electron loss. The method was used successfully to close electron, carbon, and proton balances in acetate and glucose fed microbial fuel cells. The method revealed that in the case that a substrate is loaded as pulses carbon is stored inside the cells during initial high substrate conditions and consumed during starvation, with up to 57% of the current being generated after depletion of the external carbon source. Nile blue staining of biomass samples revealed lipophilic inclusions during high substrate conditions, thus confirming the storage of polymeric material in the bacterial cells. The method also allows for indirect measurement of growth yields, which ranged from 0 to 0.54 g biomass-C formed per g substrate-C used, depending on the type of substrate and the external resistance of the circuit.

Microbial fuel cells which are operated in continuous mode are more suitable for practical applications than fed batch ones. Three influent types containing carbohydrates were tested, i.e. a glucose medium, a plant extract and artificial wastewater. The anode reactor compartment yielding the best results was a packed bed reactor containing graphite granules. While in non-mediated batch systems power outputs up to 479 W m−3 of anode compartment could be attained; in continuous mode the power outputs were limited to 49 W m−3. Cyclic voltammetry was performed to determine the potential of the in-situ synthesized bacterial redox mediators. Addition of mediators with a potential similar to the bacterial potential did not significantly alter the MFC power output, indicating a limited influence of soluble mediators for continuous microbial fuel cells. Maximum coulombic and energy conversion efficiencies were, for the continuous microbial fuel cell operating on plant extract at a loading rate of 1 kg COD m−3 of anode compartment per day, 50.3% and 26.0% respectively.

Nitrobenzene occurs as a pollutant in wastewaters originating from numerous industrial and agricultural activities. It needs to be removed prior to discharge to sewage treatment works because of its high toxicity and persistence. In this study, we investigated the use of a bioelectrochemical system (BES) to remove nitrobenzene at a cathode coupled to microbial oxidation of acetate at an anode. Effective removal of nitrobenzene at rates up to 1.29 ± 0.04 mol m−3 TCC d−1 (total cathodic compartment, TCC) was achieved with concomitant energy recovery. Correspondingly, the formation rate for the reduction product aniline was 1.14 ± 0.03 mol m−3 TCC d−1. Nitrobenzene removal and aniline formation rates were significantly enhanced when the BES was supplied with power, reaching 8.57 ± 0.03 and 6.68 ± 0.03 mol m−3 TCC d−1, respectively, at an energy consumption of 17.06 ± 0.16 W m−3 TCC (current density at 59.5 A m−3 TCC). Compared to those of conventional anaerobic biological methods for nitrobenzene removal, the required dosage of organic cosubstrate was significantly reduced in this system. Although aniline was always identified as the major product of nitrobenzene reduction at the cathode of BES in this study, the Coulombic efficiencies of nitrobenzene removal and aniline formation were dependent on the current density of the BES.

The reduction of oxygen at the cathode and the diffusion of protons from the anode to the cathode are currently perceived as two major bottlenecks of microbial fuel cells (MFCs). To address these issues, we have designed an MFC configuration in which the effluent of an acetate-fed anode was used as a feed for an aerated, biocatalysed cathode. The development of a cathodic biofilm achieved a four-fold increase of the current output compared with the non-catalysed graphite cathode, while the pH variation in the cathode compartment was reduced due to the additional transfer of protons via the liquid stream. The sequential anode-cathode configuration also provided for chemical oxygen demand (COD) polishing at the cathode by heterotrophic bacteria, with overall acetate removal consistently greater than 99%. The anode achieved an organic substrate removal of up to 2.45kg COD/m(3) of anode liquid volume per day, at Coulombic efficiencies of 65-95%. Electron balances at the cathode revealed that the main cathodic process was oxygen reduction to water with no significant Coulombic losses. The maximal power output during polarization was 110W/m(3) cathode liquid volume. The process could be operated in a stable way during more than 9 months of continuous operation. Excessive organic loading to the cathode should be avoided as it can reduce the long-term performance through the growth of heterotrophic bacteria.

Microbial fuel cells (MFCs) rely on electrochemically active bacteria to capture the chemical energy contained in organics and convert it to electrical energy. Bacteria develop biofilms on the MFC electrodes, allowing considerable conversion capacity and opportunities for extracellular electron transfer (EET). The present knowledge on EET is centred around two Gram-negative models, i.e. Shewanella and Geobacter species, as it is believed that Gram-positives cannot perform EET by themselves as the Gram-negatives can. To understand how bacteria form biofilms within MFCs and how their development, structure and viability affects electron transfer, we performed pure and co-culture experiments.Biofilm viability was maintained highest nearer the anode during closed circuit operation (current flowing), in contrast to when the anode was in open circuit (soluble electron acceptor) where viability was highest on top of the biofilm, furthest from the anode. Closed circuit anode Pseudomonas aeruginosa biofilms were considerably thinner compared to the open circuit anode (30 +/- 3 microm and 42 +/- 3 microm respectively), which is likely due to the higher energetic gain of soluble electron acceptors used. The two Gram-positive bacteria used only provided a fraction of current produced by the Gram-negative organisms. Power output of co-cultures Gram-positive Enterococcus faecium and either Gram-negative organisms, increased by 30-70% relative to the single cultures. Over time the co-culture biofilms segregated, in particular, Pseudomonas aeruginosa creating towers piercing through a thin, uniform layer of Enterococcus faecium. P. aeruginosa and E. faecium together generated a current of 1.8 +/- 0.4 mA while alone they produced 0.9 +/- 0.01 and 0.2 +/- 0.05 mA respectively.We postulate that this segregation may be an essential difference in strategy for electron transfer and substrate capture between the Gram-negative and the Gram-positive bacteria used here.

Microbial fuel cell (MFC) anodes are anaerobic bioreactors.Processes such as fermentations and methanogenesis are likely competitors to electricity generation.This work studied the pathway of glucose conversion in continuous microbial fuel cell anodes with an adapted bacterial community.The study revealed that the majority of glucose is first fermented to hydrogen and acetate.Both are then used as substrates for bacterial electricity generation.When methanogens are present, methane production occurs at a rate that slightly increases with the current.Methanogenesis and electricity generation compete for hydrogen, causing increased fermentation rates.In a rather young anodic biofilm on granular graphite, methanogenesis can be suppressed by aerating the anode compartment for one hour.Only short-term inhibition can be achieved applying the same technique on a well established biofilm on granular graphite.This study shows that fermentative processes are not detrimental to current generation, and that direct oxidation of glucose does not play a major role in mixed population conversions in a MFC anode.

Recently, bioelectrochemical systems (BESs) have emerged as a promising technology for energy and product recovery from wastewaters. To become economically viable, BESs need to (i) reach sufficient turnover rates at scale and (ii) generate a product that offsets the investment costs within a reasonable time frame. Here we used a liter scale, lamellar BES to produce a caustic solution at the cathode. The reactor was operated as a three-electrode system, in which the anode potential was fixed and power was supplied over the reactor to allow spontaneous anodic current generation. In laboratory conditions, with acetate as electron donor in the anode, the system generated up to 1.05 A (at 1.77 V applied cell voltage, 1015 A m(-3) anode volume), and allowed for the production of caustic to 3.4 wt %, at an acetate to caustic efficiency of 61%. The reactor was subsequently operated on a brewery site, directly using effluent from the brewing process. Currents of up to 0.38 A were achieved within a six-week time frame. Considerable fluctuations over weekly periods were observed, due to operational parameter changes. This study is the first to demonstrate effective production of caustic at liter scale, using BESs both in laboratory and field conditions. It also shows that input of power can easily be justified by product value.

Strategies are being developed to harvest the energy content of the wasted sludge generated from the treatment of domestic wastewater. Sludge can be hydrolysed and fermented, giving a mixture of volatile fatty acids (VFAs). Based on the composition of such a fermented stream, synthetic media were created and tested for VFA conversion in microbial fuel cells (MFCs). Mainly acetate and propionate were preferred as electron donors in the mixed VFA system, which generated a power density of 49+/-1 mW L(NAC)(-1). The other VFAs (butyrates/valerates/caproic acid) were also removed, albeit at lower rates. In single VFA tests, each VFA could be removed, but particularly i-butyrate did not provide significant current generation. PCR-DGGE indicated that the microbial community structure was highly determined by the fed VFA, rather than by the initial inoculum. The communities were dominated by Proteobacteria such as Geobacter, Comamonas, Pseudomonas and Pelobacter species. This study demonstrated the feasibility of using fatty acids, as present in fermented sludge hydrolysates, for current generation.

Reverse osmosis (RO) membranes have been successfully applied around the world for wastewater reuse applications. However, RO is a physical separation process, and besides the clean water stream (permeate) a reverse osmosis concentrate (ROC) is produced, usually representing 15-25% of the feed water flow and containing the organic and inorganic contaminants at higher concentrations. In this study, electrochemical oxidation was investigated for the treatment of ROC generated during the reclamation of municipal wastewater effluent. Using laboratory-scale two-compartment electrochemical systems, five electrode materials (i.e. titanium coated with IrO2-Ta2O5, RuO2-IrO2, Pt-IrO2, PbO2, and SnO2-Sb) were tested as anodes in batch mode experiments, using ROC from an advanced water treatment plant. The best oxidation performance was observed for Ti/Pt-IrO2 anodes, followed by the Ti/SnO2-Sb and Ti/PbO2 anodes. The effectiveness of the treatment appears to correlate with the formation of oxidants such as active chlorine (i.e. Cl2/HClO/ClO-). As a result, electro-generated chlorine led to the abundant formation of harmful by-products such as trihalomethanes (THMs) and haloacetic acids (HAAs), particularly at Ti/SnO2-Sb and Ti/Pt-IrO2 anodes. The highest concentration of total HAAs (i.e. 2.7 mg L(-1)) was measured for the Ti/SnO2-Sb electrode, after 0.55 Ah L(-1) of supplied specific electrical charge. Irrespective of the used material, electrochemical oxidation of ROC needs to be complemented by a polishing treatment to alleviate the release of halogenated by-products.

The aeration of the cathode compartment of bioelectrochemical systems (BESs) was recently shown to promote simultaneous nitrification and denitrification (SND). This study investigates the cathodic metabolism under different operating conditions as well as the structural organization of the cathodic biofilm during SND. Results show that a maximal nitrogen removal efficiency of 86.9 ± 0.5%, and a removal rate of 3.39 ± 0.08 mg NL(-1)h(-1) could be achieved at a dissolved oxygen (DO) level of 5.73 ± 0.03 mg L(-1) in the catholyte. The DO levels used in this study are higher than the thresholds previously reported as detrimental for denitrification. Analysis of the cathodic half-cell potential during batch tests suggested the existence of an oxygen gradient within the biofilm while performing SND. FISH analysis corroborated this finding revealing that the structure of the biofilm included an outer layer occupied by putative nitrifying organisms, and an inner layer where putative denitrifying organisms were most dominant. To our best knowledge this is the first time that nitrifying and denitrifying microorganisms are simultaneously observed in a cathodic biofilm.

Many microorganisms have the innate capability to discharge and/or receive electrons to and from solid state materials such as electrodes. This ability is now used towards innovative processes in wastewater treatment, power generation, production of fuels and biochemicals, bioremediation, desalination and resource recovery, among others. Despite being a dynamic field in science and technology, significant challenges remain towards industrial implementation which include representation of judicious performance indicators. This critical review outlines the progress in current density evaluated per projected surface area of electrodes, the most wide-spread performance indicator. It also proposes guidelines to correct current and exchange current per porous surface area, biofilm covered area, electrochemically- or bioelectrochemically- active surface area, of the electrodes. Recommendations for indicators to describe the environmental and electrochemical robustness of electrochemically-active biofilms are portrayed, including preservation of the predominant functionality as well as electrochemical mechanistic and phenomenological features. A few additional key elements for industrial processing are depicted. Whereas Microbial Fuel Cells (MFCs) are the main focus, some important parameters for reporting on cathodic bioproduction performance are also discussed. This critical revision aims to provide key parameters to compare the whole spectrum of microbial electrochemical systems in a consistent way.

Anaerobic digestion (AD) is a well-established technology for energy recovery from organic waste streams. Several studies noted that inserting a bioelectrochemical system (BES) inside an anaerobic digester can increase biogas output, however the mechanism behind this was not explored and primary controls were not executed. Here, we evaluated whether a BES could stabilize AD of molasses. Lab-scale digesters were operated in the presence or absence of electrodes, in open (no applied potential) and closed circuit conditions. In the control reactors without electrodes methane production decreased to 50% of the initial rate, while it remained stable in the reactors with electrodes, indicating a stabilizing effect. After 91 days of operation, the now colonized electrodes were introduced in the failing AD reactors to evaluate their remediating capacity. This resulted in an immediate increase in CH4 production and VFA removal. Although a current was generated in the BES operated in closed circuit, no direct effect of applied potential nor current was observed. A high abundance of Methanosaeta was detected on the electrodes, however irrespective of the applied cell potential. This study demonstrated that, in addition to other studies reporting only an increase in methane production, a BES can also remediate AD systems that exhibited process failure. However, the lack of difference between current driven and open circuit systems indicates that the key impact is through biomass retention, rather than electrochemical interaction with the electrodes.

During membrane treatment of secondary effluent from wastewater treatment plants, a reverse osmosis concentrate (ROC) containing trace organic contaminants is generated. As the latter are of concern, effective and economic treatment methods are required. Here, we investigated electrochemical oxidation of ROC using Ti/Ru(0.7)Ir(0.3)O(2) electrodes, focussing on the removal of dissolved organic carbon (DOC), specific ultra-violet absorbance at 254 nm (SUVA(254)), and 28 pharmaceuticals and pesticides frequently encountered in secondary treated effluents. The experiments were conducted in a continuously fed reactor at current densities (J) ranging from 1 to 250 A m(-2) anode, and a batch reactor at J = 250 A m(-2). Higher mineralization efficiency was observed during batch oxidation (e.g. 25.1 ± 2.7% DOC removal vs 0% removal in the continuous reactor after applying specific electrical charge, Q = 437.0 A h m(-3) ROC), indicating that DOC removal is depending on indirect oxidation by electrogenerated oxidants that accumulate in the bulk liquid. An initial increase and subsequent slow decrease in SUVA(254) during batch mode suggests the introduction of auxochrome substituents (e.g. -Cl, NH(2)Cl, -Br, and -OH) into the aromatic compounds. Contrarily, in the continuous reactor ring-cleaving oxidation products were generated, and SUVA(254) removal correlated with applied charge. Furthermore, 20 of the target pharmaceuticals and pesticides completely disappeared in both the continuous and batch experiments when applying J ≥ 150 A m(-2) (i.e. Q ≥ 461.5 A h m(-3)) and 437.0 A h m(-3) (J = 250 A m(-2)), respectively. Compounds that were more persistent during continuous oxidation were characterized by the presence of electrophilic groups on the aromatic ring (e.g. triclopyr) or by the absence of stronger nucleophilic substituents (e.g. ibuprofen). These pollutants were oxidized when applying higher specific electrical charge in batch mode (i.e. 1.45 kA h m(-3) ROC). However, baseline toxicity as determined by Vibrio fischeri bioluminescence inhibition tests (Microtox) was increasing with higher applied charge during batch and continuous oxidation, indicating the formation of toxic oxidation products, possibly chlorinated and brominated organic compounds.

Reverse osmosis concentrate from wastewater reclamation contains biorefractory trace organic contaminants that may pose environmental or health hazard. Due to its high conductivity, electrochemical oxidation of brine requires low voltage which is energetically favourable. However, the presence of chloride ions may lead to the formation of chlorinated by-products, which are likely to exert an increased toxicity and persistence to further oxidation than their non-chlorinated analogues. Here, the performance of Ti/Pt–IrO2, Ti/SnO2–Sb and Si/BDD anodes was evaluated for the electrochemical oxidation of ROC in the presence of chloride, nitrate or sulfate ions (0.05 M sodium salts). In order to investigate the electrooxidation of ROC with nitrate and sulfate ions as dominant ion mediators, chloride ion concentration was decreased 10 times by electrodialytic pretreatment. The highest Coulombic efficiency for chemical oxygen demand (COD) removal was observed in the presence of high chloride ions concentration for all anodes tested (8.3–15.9%). Electrooxidation of the electrodialysed concentrate at Ti/SnO2–Sb and Ti/Pt–IrO2 electrodes exhibited low dissolved organic carbon (DOC) (i.e. 23 and 12%, respectively) and COD removal (i.e. 37–43 and 6–22%, respectively), indicating that for these electrodes chlorine-mediated oxidation was the main oxidation mechanism, particularly in the latter case. In contrast, DOC removal for the electrodialysed concentrate stream was enhanced at Si/BDD anode in the presence of SO42− (i.e. 51%) compared to NO32− electrolyte (i.e. 41%), likely due to the contribution of SO4·− and S2O82− species to the oxidative degradation. Furthermore, decreased concentration of chloride ions lead to a lower formation of haloacetic acids and trihalomethanes at all three electrodes tested.

Abstract Microbial fuel cells (MFCs) have applications other than electricity production, including the capacity to power desirable reactions in the cathode chamber. However, current knowledge of the microbial ecology and physiology of biocathodes is minimal, and as a result more research dedicated to understanding the microbial communities active in cathode biofilms is required. Here we characterize the microbiology of denitrifying bacterial communities stimulated by reducing equivalents generated from the anodic oxidation of acetate. We analyzed biofilms isolated from two types of cathodic denitrification systems: (1) a loop format where the effluent from the carbon oxidation step in the anode is subjected to a nitrifying reactor which is fed to the cathode chamber and (2) an alternative non-loop format where anodic and cathodic feed streams are separated. The results of our study indicate the superior performance of the loop reactor in terms of enhanced current production and nitrate removal rates. We hypothesized that phylogenetic or structural features of the microbial communities could explain the increased performance of the loop reactor. We used PhyloChip with 16S rRNA (cDNA) and fluorescent in situ hybridization to characterize the active bacterial communities. Our study results reveal a greater richness, as well as an increased phylogenetic diversity, active in denitrifying biofilms than was previously identified in cathodic systems. Specifically, we identified Proteobacteria, Firmicutes and Chloroflexi members that were dominant in denitrifying cathodes. In addition, our study results indicate that it is the structural component, in terms of bacterial richness and evenness, rather than the phylogenetic affiliation of dominant bacteria, that best corresponds to cathode performance.

Summary In many microbial bioreactors, high shear rates result in strong attachment of microbes and dense biofilms. In this study, high shear rates were applied to enrich an anodophilic microbial consortium in a microbial fuel cell (MFC). Enrichment at a shear rate of about 120 s −1 resulted in the production of a current and power output two to three times higher than those in the case of low shear rates (around 0.3 s −1 ). Biomass and biofilm analyses showed that the anodic biofilm from the MFC enriched under high shear rate conditions, in comparison with that under low shear rate conditions, had a doubled average thickness and the biomass density increased with a factor 5. The microbial community of the former, as analysed by DGGE, was significantly different from that of the latter. The results showed that enrichment by applying high shear rates in an MFC can result in a specific electrochemically active biofilm that is thicker and denser and attaches better, and hence has a better performance.

Electricity-driven bioproduction processes such as microbial electrosynthesis enable converting CO2 and organic feedstocks into target chemicals with minimal addition of external chemicals. Bioelectrochemical CO2 conversion to (mainly) acetate has mostly been demonstrated in batch processes. Continuous reactor operation and the operational parameters associated with it have received limited attention. Here, we demonstrate that improving bioelectrochemical reactor design to a higher cathode surface to volume ratio results in an enhanced acetate titer; 5.7 ± 0.74 g L−1 (11.5 ± 6.6 g m−2 d−1) in galvanostastically controlled (−5 A m−2cathode) batch reactors with a mixed microbial community. A long-term and stable bioproduction process could be established in which hydraulic residence time (HRT) affected the product patterns as well as the acetate production rate, up to 21 g m−2 d−1 for an HRT of 3.3d (63% coulombic efficiency) was achieved; the highest reported thus far in a continuous process. The specific energy input per kilogram of acetic acid produced during batch and continuous processes (HRT: 3.3d) was 29 ± 0.7 and 16 ± 1.3 kWhel kg−1, respectively. Butyrate and isopropanol were the other major biochemicals produced at maximum rates of 3.7 and 3.3 g m−2 d−1 (18.6% and 21.8% of the electrons, respectively) leading to titers of 0.67 and 0.82 g L−1 during the continuous process. This is the first report on the production of a secondary alcohol (isopropanol), using a mixed culture, in CO2 fed systems. The product ratios between these organics could be steered based on operational pH and HRTs. Operating reactors at an HRT of 5 d at pH 5 led to stable production of butyrate (1.9 ± 0.6 g m−2 d−1) and isopropanol (1.17 ± 0.34 g m−2 d−1). Cyclic voltammetry suggested an “ennoblement” of the cathode over time, shifting the onset for reductive current by more than 150 mV. Microbial community analysis revealed Acetobacterium as the main bacterial group involved in CO2 reduction to acetate, and the presence of diverse bacterial groups in response to different operational conditions.

Most of the existing sulfide removal processes from wastewaters and waste gases require substantial amounts of energy inputs. Here we present an electrochemical method by means of a fuel cell that removes sulfide while producing energy. A lab scale fuel cell was operated at ambient temperature and neutral pH, which was capable of removing aqueous sulfide continuously for 2 months at a rate of 0.62+/-0.1 kg S m(-3)d(-1) of net anodic compartment (NAC) (0.28+/-0.05 kg S m(-3)d(-1) of total anodic compartment, TAC). During continuous operation, on average, the power generated was 12+/-2 W m(-3) NAC (5+/-1 W m(-3) TAC), with a maximum capacity of the cell of 166 W m(-3) NAC (74 W m(-3) TAC). Potassium ferricyanide was used as cathodic electron acceptor. Elemental sulfur was identified as the predominant final oxidation product that was deposited on the anode. In this abiotic fuel cell, the sulfide oxidation rate was not diminished by the presence of an organic electron donor (acetate) during batch experiments while the acetate concentration remained unchanged. This is particularly important for selective sulfide removal from wastewater where organics are essential for downstream nutrient removal. Elemental sulfur deposited on the anode appeared to limit the operation of the fuel cell after 3 months of operation, necessitating periodic removal of the accumulated sulfur from the electrode.

Biocatalyzed electrolysis is a microbial fuel cell based technology for the generation of hydrogen gas and other reduced products out of electron donors. Examples of electron donors are acetate and wastewater. An external power supply can support the process and therefore circumvent thermodynamical constraints that normally render the generation of compounds such as hydrogen unlikely. We have investigated the possibility of biocatalyzed electrolysis for the generation of methane. The cathodically produced hydrogen could be converted into methane at a ratio of 0.41 mole methane mole(-1) acetate, at temperatures of 22+/-2 degrees C. The anodic oxidation of acetate was not hampered by ammonium concentrations up to 5 g N L(-1). An overview is given of potential applications for biocatalyzed electrolysis.

The electron recovery in microbial fuel cells (MFCs) is decreased by processes like methanogenesis, bacterial growth, and the accumulation of intermediates. Using a suite of analytical techniques, including electrochemical monitoring, chemical analysis, microsensor analysis, and Titration and Off-Gas Analysis (TOGA), this study aimed to (a) identify and quantify the electron losses occurring at the anode and the cathode of a MFC removing acetate and nitrate (NO3-), respectively, and (b) to investigate the impact of the operational characteristics of the cathode on the denitrification process. Our results show that methane (CH4) production and estimated biomass formation at the anode and nitrous oxide (N2O) accumulation at the cathode were responsible for the reduction of Coulombic efficiency (epsilon) during continuous feeding conditions. At the anode, up to 40.1% of the acetate consumed was released as methane at closed circuit. At the cathode, N2O accumulation represented instead the main loss accounting for up to 10.0 +/- 2.1% of the oxidation capacity of the electron acceptor provided as NO3-. Batch experiments at controlled potentials and currents revealed that for a given current the fraction of electron transferred and released as N2O is significantly reduced by low cathodic potentials.

Stainless steel (SS) can be an attractive material to create large electrodes for microbial bioelectrochemical systems (BESs), due to its low cost and high conductivity. However, poor biocompatibility limits its successful application today. Here we report a simple and effective method to make SS electrodes biocompatible by means of flame oxidation. Physicochemical characterization of electrode surface indicated that iron oxide nanoparticles (IONPs) were generated in situ on an SS felt surface by flame oxidation. IONPs-coating dramatically enhanced the biocompatibility of SS felt and consequently resulted in a robust electroactive biofilm formation at its surface in BESs. The maximum current densities reached at IONPs-coated SS felt electrodes were 16.5 times and 4.8 times higher than the untreated SS felts and carbon felts, respectively. Furthermore, the maximum current density achieved with the IONPs-coated SS felt (1.92 mA/cm(2), 27.42 mA/cm(3)) is one of the highest current densities reported thus far. These results demonstrate for the first time that flame oxidized SS felts could be a good alternative to carbon-based electrodes for achieving high current densities in BESs. Most importantly, high conductivity, excellent mechanical strength, strong chemical stability, large specific surface area, and comparatively low cost of flame oxidized SS felts offer exciting opportunities for scaling-up of the anodes for BESs.

We had extracted n-caproate from bioreactor broth. Here, we introduced in-line membrane electrolysis that utilized a pH gradient between two chambers to transfer the product into undissociated n-caproic acid without chemical addition. Due to the low maximum solubility of this acid, selective phase separation occurred, allowing simple product separation into an oily liquid containing ∼90% n-caproic and n-caprylic acid.

The bio-based economy relies on sustainable, plant-derived resources for fuels, chemicals, materials, food and feed rather than on the evanescent usage of fossil resources.The cornerstone of this economy is the biorefinery, in which renewable resources are intelligently converted to a plethora of products, maximizing the valorization of the feedstocks.Innovation is a prerequisite to move a fossil-based economy toward sustainable alternatives, and the viability of the bio-based economy depends on the integration between plant (green) and industrial (white) biotechnology.Green biotechnology deals with primary production through the improvement of biomass crops, while white biotechnology deals with the conversion of biomass into products and energy.Waste streams are minimized during these processes or partly converted to biogas, which can be used to power the processing pipeline.The sustainability of this economy is guaranteed by a third technology pillar that uses thermochemical conversion to valorize waste streams and fix residual carbon as biochar in the soil, hence creating a carbon-negative cycle.These three different multidisciplinary pillars interact through the value chain of the bio-based economy.

Human urine contains high concentrations of nitrogen, contributing about 75% of the nitrogen in municipal wastewaters yet only 1% of the volume. Source separation of urine produces an ideal waste stream for nitrogen and phosphorus recovery, reducing downstream costs of nutrient treatment at wastewater treatment facilities. We examined the efficiency and feasibility of ammonia extraction and recovery from synthetic and undiluted human urine using an electrochemical cell (EC). EC processing of synthetic urine produced an ammonium flux of 384 ± 8 g N m−2 d−1 with a 61 ± 1% current efficiency at an energy input of 12 kWh kg−1 N removed. EC processing of real urine displayed similar performance, with an average ammonium flux of 275 ± 5 g N m−2 d−1 sustained over 10 days with 55 ± 1% current efficiency for ammonia and at an energy input of 13 kWh kg−1 N removed. With the incorporation of an ammonia stripping and absorption unit into the real urine system, 57 ± 0.5% of the total nitrogen was recovered as ammonium sulfate. A system configuration additionally incorporating stripping of the influent headspace increased total nitrogen recovery to 79% but led to reduced performance of the EC as the urine ammonium concentration decrease. Direct stripping of ammonia (NH3) from urine with no chemical addition achieved only 12% total nitrogen recovery at hydraulic retention times comparable with the EC systems. Our results demonstrate that ammonia can be extracted via electrochemical means at reasonable energy inputs of approximately 12 kWh kg−1 N. Considering also that the hydrogen generated is worth 4.3 kWh kg−1 N, the net electrical input for extraction becomes approximately 8 kWh kg−1 N if the hydrogen can be used. Critical for further development will be the inclusion of a passive means for ammonia stripping to reduce additional energy inputs.

Annually, thousands of oil spills occur across the globe. As a result, petroleum substances and petrochemical compounds are widespread contaminants causing concern due to their toxicity and recalcitrance. Many remediation strategies have been developed using both physicochemical and biological approaches. Biological strategies are most benign, aiming to enhance microbial metabolic activities by supplying limiting inorganic nutrients, electron acceptors or donors, thus stimulating oxidation or reduction of contaminants. A key issue is controlling the supply of electron donors/acceptors. Bioelectrochemical systems (BES) have emerged, in which an electrical current serves as either electron donor or acceptor for oil spill bioremediation. BES are highly controllable and can possibly also serve as biosensors for real time monitoring of the degradation process. Despite being promising, multiple aspects need to be considered to make BES suitable for field applications including system design, electrode materials, operational parameters, mode of action and radius of influence. The microbiological processes, involved in bioelectrochemical contaminant degradation, are currently not fully understood, particularly in relation to electron transfer mechanisms. Especially in sulfate rich environments, the sulfur cycle appears pivotal during hydrocarbon oxidation. This review provides a comprehensive analysis of the research on bioelectrochemical remediation of oil spills and of the key parameters involved in the process.

Our understanding of the complex interconnected processes performed by microbial communities is hindered by our inability to culture the vast majority of microorganisms. Metagenomics provides a way to bypass this cultivation bottleneck and recent advances in this field now allow us to recover a growing number of genomes representing previously uncultured populations from increasingly complex environments. In this study, a temporal genome-centric metagenomic analysis was performed of lab-scale anaerobic digesters that host complex microbial communities fulfilling a series of interlinked metabolic processes to enable the conversion of cellulose to methane. In total, 101 population genomes that were moderate to near-complete were recovered based primarily on differential coverage binning. These populations span 19 phyla, represent mostly novel species and expand the genomic coverage of several rare phyla. Classification into functional guilds based on their metabolic potential revealed metabolic networks with a high level of functional redundancy as well as niche specialization, and allowed us to identify potential roles such as hydrolytic specialists for several rare, uncultured populations. Genome-centric analyses of complex microbial communities across diverse environments provide the key to understanding the phylogenetic and metabolic diversity of these interactive communities.

Raw metals are fundamental to the global economy as they are essential to maintain the quality of our life as well as industrial performance. A number of metal-bearing aqueous matrices are appealing as alternative supplies to conventional mining, like solid industrial and urban waste leachates, wastewaters and even some natural extreme environments (e.g. deep marine sediments, geothermal brines). Some of these sources are already managed for recovery, while others are not suitable either because they are too low in content of recoverable metals or they contain too many impurities that would interfere with classical recovery processes or would be cost-prohibitive. Microbial electro-metallurgy, which results from the interactions between microorganisms, metals and electrodes, in which the electron transfer chain associated with microbial respiration plays a key role, can contribute to overcome these challenges. This review provides the state of the art on this subject, and summarizes the general routes through which microbes can catalyse or support metal recovery, leading to nano- and macro-scale materials. Competing sorption and electrochemical technologies are briefly revisited. The relevant sources of metals are highlighted as well as the challenges and opportunities to turn microbial electro-metallurgy into a sustainable industrial technology in the near future. Finally, an outlook to pursue functional materials through microbial electrometallurgy is provided.

For over a century, anaerobic digestion has been a key technology in stabilizing organic waste streams, while at the same time enabling the recovery of energy. The anticipated transition to a bio-based economy will only increase the quantity and diversity of organic waste streams to be treated, and, at the same time, increase the demand for additional and effective resource recovery schemes for nutrients and organic matter. The performance of anaerobic digestion can be supported and enhanced by (bio)electrochemical systems in a wide variety of hybrid technologies. Here, the possible benefits of combining anaerobic digestion with (bio)electrochemical systems were reviewed in terms of (1) process monitoring, control, and stabilization, (2) nutrient recovery, (3) effluent polishing, and (4) biogas upgrading. The interaction between microorganisms and electrodes with respect to niche creation is discussed, and the potential impact of this interaction on process performance is evaluated. The strength of combining anaerobic digestion with (bio)electrochemical technologies resides in the complementary character of both technologies, and this perspective was used to distinguish transient trends from schemes with potential for full-scale application. This is supported by an operational costs assessment, showing that the economic potential of combining anaerobic digestion with a (bio)electrochemical system is highly case-specific, and strongly depends on engineering challenges with respect to full-scale applications.

Abstract Anaerobic digestion is a widely used technology for waste stabilization and generation of biogas and has recently emerged as a potentially important process for the production of high value volatile fatty acids (VFAs) and alcohols. Here, three reactors were seeded with inoculum from a stably performing methanogenic digester and selective operating conditions (37°C and 55°C; 12 day and 4 day solids retention time) were applied to restrict methanogenesis while maintaining hydrolysis and fermentation. Replicated experiments performed at each set of operating conditions led to reproducible VFA production profiles which could be correlated with specific changes in microbial community composition. The mesophilic reactor at short solids retention time showed accumulation of propionate and acetate (42 ± 2% and 15 ± 6% of COD hydrolyzed , respectively) and dominance of Fibrobacter and Bacteroidales . Acetate accumulation (>50% of COD hydrolyzed ) was also observed in the thermophilic reactors, which were dominated by Clostridium . Under all tested conditions, there was a shift from acetoclastic to hydrogenotrophic methanogenesis and a reduction in methane production by >50% of COD hydrolyzed . Our results demonstrate that shortening the SRT and increasing the temperature are effective strategies for driving microbial communities towards controlled production of high levels of specific volatile fatty acids.

Practical application of microbial electrolysis cells (MECs) for hydrogen production requires scalable reactors with low internal resistance, high current density, and high hydrogen recovery. This work reports a liter scale tubular MEC approaching these requirements. The tubular cell components (a platinum-coated titanium mesh cathode, an anion exchange membrane, and a pleated stainless steel felt anode) were arranged in a concentric configuration. The reactor had a low internal resistance (0.325 Ω, 19.5 mΩ m2) due to the high conductivity of the electrodes, a compact reactor configuration, and proper mixing. With acetate as electron donor, the MEC achieved a volumetric current density of 654 ± 22 mA L−1 (projected current density, 1.09 ± 0.04 mA cm−2) and a volumetric hydrogen production rate of 7.10 ± 0.01 L L−1 d−1 at an applied voltage of 1 V. The reactor also showed high hydrogen recovery (∼100%), high hydrogen purity (>98%), and excellent operational stability during the 3 weeks of operation. These results demonstrated that high hydrogen production rate could be achieved on larger scale MEC and this tubular MEC holds great potential for scaling up.

Acetate and ethanol can be converted to caproic acid by microorganisms through reverse β-oxidation. There is limited insight into the versatility of chain elongation in view of different starting substrates, including even- and odd-carbon carboxylates and alcohols other than ethanol. Thermodynamic analyses show that most elongation pathways are energetically feasible. Through incubations of microbial communities with different substrate-pair combinations, we established that ethanol and propanol were both highly suitable for chain elongation. As an electron acceptor, acetate, propionate, and butyrate readily elongated with ethanol, whereas an adaptation period was necessary for formate. Isobutyrate and longer-chained fatty acids above butyrate were not elongated. The microbial communities converged, and consistent enrichment of Clostridium spp. was observed, independent of the supplied alcohol or carboxylate, with a strain related to Clostridium kluyveri dominating the enrichments. Community analysis also showed phylotypes related to Bacteroidaceae and Microbacteriaceae families in all tests that are capable of converting the base substrates to useful intermediates. These organisms were mainly enriched with methanol or formate. Our overall conclusion is thus that multiple substrates can be used for chain elongation and that this process is carried out by highly similar organisms for direct chain elongation irrespective of the substrate.

Biochars have gathered considerable interest for agronomic and engineering applications. In addition to their high sorption ability, biochars have been shown to accept or donate considerable amounts of electrons to/from their environment via abiotic or microbial processes. Here, we measured the electron accepting (EAC) and electron donating (EDC) capacities of wood-based biochars pyrolyzed at three different highest treatment temperatures (HTTs: 400, 500, 600 °C) via hydrodynamic electrochemical techniques using a rotating disc electrode. EACs and EDCs varied with HTT in accordance with a previous report with a maximal EAC at 500 °C (0.4 mmol(e(-)).gchar(-1)) and a large decrease of EDC with HTT. However, while we monitored similar EAC values than in the preceding study, we show that the EDCs have been underestimated by at least 1 order of magnitude, up to 7 mmol(e(-)).gchar(-1) for a HTT of 400 °C. We attribute this existing underestimation to unnoticed slow kinetics of electron transfer from biochars to the dissolved redox mediators used in the monitoring. The EDC of other soil organic constituents such as humic substances may also have been underestimated. These results imply that the redox properties of biochars may have a much bigger impact on soil biogeochemical processes than previously conjectured.

Methane (CH4) release from wetlands is an important source of greenhouse gas emissions. Gas exchange occurs mainly through the aerenchyma of plants, and production of greenhouse gases is heavily dependent on rhizosphere biogeochemical conditions (i.e. substrate availability and redox potential). It is hypothesized that by introducing a biocatalyzed anode electrode in the rhizosphere of wetland plants, a competition for carbon and electrons can be invoked between electrical current-generating bacteria and methanogenic Archaea. The anode electrode is part of a bioelectrochemical system (BES) capable of harvesting electrical current from microbial metabolism. In this work, the anode of a BES was introduced in the rhizosphere of rice plants (Oryza sativa), and the impact on methane emissions was monitored. Microbial current generation was able to outcompete methanogenic processes when the bulk matrix contained low concentrations of organic carbon, provided that the electrical circuit with the effective electroactive microorganisms was in place. When interrupting the electrical circuit or supplying an excess of organic carbon, methanogenic metabolism was able to outcompete current generating metabolism. The qPCR results showed hydrogenotrophic methanogens were the most abundant methanogenic group present, while mixotrophic or acetoclastic methanogens were hardly detected in the bulk rhizosphere or on the electrodes. Competition for electron donor and acceptor were likely the main drivers to lower methane emissions. Overall, electrical current generation with BESs is an interesting option to control CH4 emissions from wetlands but needs to be applied in combination with other mitigation strategies to be successful and feasible in practice.

Electrochemically active biofilms rely on microorganisms capable of extracellular electron transfer. Such biofilms are involved in the dissimilatory reduction of metal oxides in natural environments as well as electricity driving and driven processes at the electrodes of microbial bioelectrochemical systems. In this work we present the application of confocal Raman microscopy (CRM) as a non-invasive, label-free, and in vivo characterization method of acetate oxidizing anodic biofilms, grown from primary wastewater inoculum and dominated by Geobacter species (>85% of sequences analysed using pyrotag sequencing). Using the resonance Raman effect of the heme protein cytochrome c (Cyt c)—an ubiquitous component of extracellular electron transfer reactions—it was possible to collect characteristic spectral information of electrochemically active biofilms at pixel integration times of 0.2 s and an excitation wavelength of 532 nm. This allowed monitoring of biofilm development at different growth stages, without impacting its structural or metabolic activity. Furthermore, we demonstrate the possibility of non-invasive investigation of the spatial redox electrochemistry (up to a compositional level) of electrochemically active biofilms, as we observed significant changes in the vibrational properties of Cyt c resulting from shifts in the anodic potential between different redox conditions. Compared to conventional methods requiring destructive sample manipulation and fixation, the proposed approach based on CRM allows the non-invasive analysis of microbial aggregates with minimal sample preparation or prior knowledge of the sample.

Short-chain carboxylates such as acetate are easily produced through mixed culture fermentation of many biological waste streams, although routinely digested to biogas and combusted rather than harvested. We developed a pipeline to extract and upgrade short-chain carboxylates to esters via membrane electrolysis and biphasic esterification. Carboxylate-rich broths are electrolyzed in a cathodic chamber from which anions flux across an anion exchange membrane into an anodic chamber, resulting in a clean acid concentrate with neither solids nor biomass. Next, the aqueous carboxylic acid concentrate reacts with added alcohol in a water-excluding phase to generate volatile esters. In a batch extraction, 96 ± 1.6% of the total acetate was extracted in 48 h from biorefinery thin stillage (5 g L–1 acetate) at 379 g m–2 d–1 (36% Coulombic efficiency). With continuously regenerated thin stillage, the anolyte was concentrated to 14 g/L acetic acid, and converted at 2.64 g (acetate) L–1 h–1 in the first hour to ethyl acetate by the addition of excess ethanol and heating to 70 °C, with a final total conversion of 58 ± 3%. This processing pipeline enables direct production of fine chemicals following undefined mixed culture fermentation, embedding carbon in industrial chemicals rather than returning them to the atmosphere as carbon dioxide.

Rare earth elements (REEs) have become increasingly important in modern day technologies. Unfortunately, their recycling is currently limited, and the conventional technologies for their extraction and purification are exceedingly energy and chemical intensive. New sustainable technologies for REE extraction from both primary and secondary resources would be extremely beneficial. This research investigated a two-stage recovery strategy focused on the recovery of neodymium (Nd) and lanthanum (La) from monazite ore that combines microbially based leaching (using citric acid and spent fungal supernatant) with electrochemical extraction. Pretreating the phosphate-based monazite rock (via roasting) dramatically increased the microbial REE leaching efficiency. Batch experiments demonstrated the effective and continued leaching of REEs by recycled citric acid, with up to 392 mg of Nd L-1 and 281 mg of La L-1 leached during seven consecutive 24 h cycles. Neodymium was further extracted in the catholyte of a three-compartment electrochemical system, with up to 880 mg of Nd L-1 achieved within 4 days (at 40 A m-2). Meanwhile, the radioactive element thorium and counterions phosphate and citrate were separated effectively from the REEs in the anolyte, favoring REE extraction and allowing sustainable reuse of the leaching agent. This study shows a promising technology that is suitable for primary ores and can further be optimized for secondary resources.

Nickel porous hollow fibers coated with CNTs acted as both a gas transfer membrane for CO₂delivery and a cathode for providing electrons to microbial catalysts, achieving improved CO₂conversion to value-added products in microbial electrosynthesis.

This critical review outlines a roadmap for the conversion of chemical oxygen demand (COD) contained in sewage to commodities based on three-steps: capture COD as sludge, ferment it to volatile fatty acids (VFA), and upgrade VFA to products.The article analyzes the state-ofthe-art of this three-step approach and discusses the bottlenecks and challenges.The potential of this approach is illustrated for the European Union's 28 member states (EU-28) through Monte Carlo simulations.High-rate contact stabilization captures the highest amount of COD (66-86 gCOD person equivalent -1 day -1 in 60% of the iterations).Combined with thermal hydrolysis, this would lead to a VFA-yield of 23-44 gCOD person equivalent -1 day -1 .Upgrading VFA generated by the EU-28 would allow, in 60% of the simulations, for a yearly production of 0.2-2.0megatonnes of esters, 0.7-1.4megatonnes of polyhydroxyalkanoates or 0.6-2.2megatonnes of microbial protein substituting, respectively, 20-273%, 70-140% or 21-72% of their global counterparts (i.e.. petrochemical-based esters, bioplastics or fishmeal).From these flows, we conclude that sewage holds a strong potential as biorefinery feedstock, although research is needed to enhance capture, fermentation and upgrading efficiencies.These developments need to be supported by economic/environmental analyses and policies that incentivize a more sustainable management of our resources.

The product of current syngas fermentation systems is an ethanol/acetic acid mixture and the goal is to maximize ethanol recovery. However, ethanol currently has a relatively low market value and its separation from the fermentation broth is energy intensive. We can circumvent these disadvantages of ethanol production by converting the dilute ethanol/acetic acid mixture into products with longer carbon backbones, which are of higher value and are more easily extracted than ethanol. Chain elongation, which is the bioprocess in which ethanol is used to elongate short-chain carboxylic acids to medium-chain carboxylic acids (MCCAs), has been studied with pure cultures and open cultures of microbial consortia (microbiomes) with several different substrates. While upgrading syngas fermentation effluent has been studied with open cultures, to our knowledge, no study exists that has performed this with pure cultures.Here, pure cultures of Clostridium kluyveri were used in continuous bioreactors to convert ethanol/acetic acid mixtures into MCCAs. Besides changing the operating conditions in regards to substrate loading rates and composition, the effect of in-line product extraction, pH, and the use of real syngas fermentation effluent on production rates were tested. Increasing the organic loading rates resulted in proportionally higher production rates of n-caproic acid, which were up to 40 mM day-1 (4.64 g L-1 day-1) at carbon conversion efficiencies of 90% or higher. The production rates were similar for bioreactors with and without in-line product extraction. Furthermore, a lower ethanol/acetic acid ratio (3:1 instead of 10:1) enabled faster and more efficient n-caproic acid production. In addition, n-caprylic acid production was observed for the first time with C. kluyveri (up to 2.19 ± 0.34 mM in batch). Finally, the use of real effluent from syngas fermentation, without added yeast extract, but with added defined growth factors, did maintain similar production rates. Throughout the operating period, we observed that the metabolism of C. kluyveri was inhibited at a mildly acidic pH value of 5.5 compared to a pH value of 7.0, while reactor microbiomes perform successfully at mildly acidic conditions.Clostridium kluyveri can be used as a biocatalyst to upgrade syngas fermentation effluent into MCCAs at pH values above 5.5.

Volatile fatty acids (VFA) are building blocks for the chemical industry. Sustainable, biological production is constrained by production and recovery costs, including the need for intensive pH correction. Membrane electrolysis has been developed as an in situ extraction technology tailored to the direct recovery of VFA from fermentation while stabilizing acidogenesis without caustic addition. A current applied across an anion exchange membrane reduces the fermentation broth (catholyte, water reduction: H2O + e(-) → ½ H2 + OH(-)) and drives carboxylate ions into a clean, concentrated VFA stream (anolyte, water oxidation: H2O → 2e(-) + 2 H(+) + O2).In this study, we fermented thin stillage to generate a mixed VFA extract without chemical pH control. Membrane electrolysis (0.1 A, 3.22 ± 0.60 V) extracted 28 ± 6 % of carboxylates generated per day (on a carbon basis) and completely replaced caustic control of pH, with no impact on the total carboxylate production amount or rate. Hydrogen generated from the applied current shifted the fermentation outcome from predominantly C2 and C3 VFA (64 ± 3 % of the total VFA present in the control) to majority of C4 to C6 (70 ± 12 % in the experiment), with identical proportions in the VFA acid extract. A strain related to Megasphaera elsdenii (maximum abundance of 57 %), a bacteria capable of producing mid-chain VFA at a high rate, was enriched by the applied current, alongside a stable community of Lactobacillus spp. (10 %), enabling chain elongation of VFA through lactic acid. A conversion of 30 ± 5 % VFA produced per sCOD fed (60 ± 10 % of the reactive fraction) was achieved, with a 50 ± 6 % reduction in suspended solids likely by electro-coagulation.VFA can be extracted directly from a fermentation broth by membrane electrolysis. The electrolytic water reduction products are utilized in the fermentation: OH(-) is used for pH control without added chemicals, and H2 is metabolized by species such as Megasphaera elsdenii to produce greater value, more reduced VFA. Electro-fermentation displays promise for generating added value chemical co-products from biorefinery sidestreams and wastes.

Lack of suitable electron donors or acceptors is in many cases the key reason for pollutants to persist in the environment. Externally supplementation of electron donors or acceptors is often difficult to control and/or involves chemical additions with limited lifespan, residue formation or other adverse side effects. Microbial electrochemistry has evolved very fast in the past years - this field relates to the study of electrochemical interactions between microorganisms and solid-state electron donors or acceptors. Current can be supplied in such so-called bioelectrochemical systems (BESs) at low voltage to provide or extract electrons in a very precise manner. A plethora of metabolisms can be linked to electrical current now, from metals reductions to denitrification and dechlorination. In this perspective, we provide an overview of the emerging applications of BES and derived technologies towards the bioremediation field and outline how this approach can be game changing.

Conventional plant and meat protein production have low nitrogen usage efficiencies and high energy needs.Microbial protein (MP) is an alternative that offers higher nitrogen conversion efficiencies with low energy needs if nitrogen is recovered from a concentrated waste source such as source-separated urine.An electrochemical cell (EC) was optimized for ammonia recovery as NH 3 /H 2 gas mixtures usable for MP production.Undiluted hydrolyzed urine was fed to the caustic-generating cathode compartment for ammonia stripping with redirection to the anode compartment for additional ammonium extraction.Using synthetic urine at 48 A m -2 the nitrogen removal efficiency reached 91.6 ± 2.1%.Tests with real urine at 20 A m -2 , achieved 87.1 ± 6.0% and 68.4 ± 14.6% requiring 5.8 and 13.9 kWh kg N -1 recovered, via absorption in acid or MP medium, respectively.Energy savings through accompanying electrolytic H 2 and O 2 production were accounted for.Subsequently, MP was grown in fed-batch on MP medium with conventional NH 4 + or urine-derived NH 3 yielding 3.74 ± 1.79 and 4.44 ± 1.59 g CDW L -1 , respectively.Dissolution of gaseous NH 3 in MP medium maintained neutral pH in the MP reactor preventing caustic addition and thus salt accumulation.Urine-nitrogen could thus be valorized as MP via electrochemical ammonia recovery.

Coupling decentralized biomethane generation to centralized CO production <italic>via</italic> gas grid redistribution can be an economically viable CO₂ utilization strategy.

The Haber Bosch process is among the greatest inventions of the 20th century. It provided agriculture with reactive nitrogen and ultimately mankind with nourishment for a population of 7 billion people. However, the present agricultural practice of growing crops for animal production and human food constitutes a major threat to the sustainability of the planet in terms of reactive nitrogen pollution. In view of the shortage of directly feasible and cost-effective measures to avoid these planetary nitrogen burdens and the necessity to remediate this problem, we foresee the absolute need for and expect a revolution in the use of microbes as a source of protein. Bypassing land-based agriculture through direct use of Haber Bosch produced nitrogen for reactor-based production of microbial protein can be an inspiring concept for the production of high quality animal feed and even straightforward supply of proteinaceous products for human food, without significant nitrogen losses to the environment and without the need for genetic engineering to safeguard feed and food supply for the generations to come.

Carbohydrate-rich waste streams can be used for bioproduction of medium-chain carboxylic acids (MCCA) such as caproic acid. The carbohydrates in these streams can be converted to lactic acid as the initial fermentation product, which can then be fermented to MCCA by chain elongation. In this process, chain elongators compete for lactic acid with other bacterial groups that, for instance, ferment lactic acid to propionic and acetic acid. Understanding the drivers that control the competition between these two pathways is essential to maximizing MCCA production. This study aimed to investigate the competition between chain elongating and propionic acid producing organisms as a function of operational pH. Operation of long-term lactic acid fermenting reactors with varying pH values showed that pH values above 6 resulted in a propionic acid producing community dominated by Veillonella and Aminobacterium. At pH values below 6, the community moved towards chain elongation, with communities dominated by Caproiciproducens. Short-term incubations showed that rates of lactic acid consumption were strongly reduced at pH below 6 (7.7 ± 1.2 mM lactic acid·h−1 at pH 6.5; 0.74 ± 0.33 mM lactic acid·h−1 at pH 5.5). Similar to observations in long-term reactors, when a chain elongating community adapted to pH 5.5 was used for short-term incubations at pH 6.5, propionic acid was the dominant product. The results of this study show that pH below 6 stimulate lactic acid chain elongators through kinetic effects, and potentially improved energetics, providing a tool for microbial management of MCCA-producing systems.

Pseudomonas putida is a promising host for the bioproduction of chemicals, but its industrial applications are significantly limited by its obligate aerobic character. The aim of this paper is to empower the anoxic metabolism of wild-type Pseudomonas putida to enable bioproduction anaerobically, with the redox power from a bioelectrochemical system (BES).The obligate aerobe Pseudomonas putida F1 was able to survive and produce almost exclusively 2-Keto-gluconate from glucose under anoxic conditions due to redox balancing with electron mediators in a BES. 2-Keto-gluconate, a precursor for industrial anti-oxidant production, was produced at an overall carbon yield of over 90 % based on glucose. Seven different mediator compounds were tested, and only those with redox potential above 0.207 V (vs standard hydrogen electrode) showed interaction with the cells. The productivity increased with the increasing redox potential of the mediator, indicating this was a key factor affecting the anoxic production process. P. putida cells survived under anaerobic conditions, and limited biofilm formation could be observed on the anode's surface. Analysis of the intracellular pools of ATP, ADP and AMP showed that cells had an increased adenylate energy charge suggesting that cells were able to generate energy using the anode as terminal electron acceptor. The analysis of NAD(H) and NADP(H) showed that in the presence of specific extracellular electron acceptors, the NADP(H) pool was more oxidised, while the NAD(H) pool was unchanged. This implies a growth limitation under anaerobic conditions due to a shortage of NADPH and provides a way to limit biomass formation, while allowing cell maintenance and catalysis at high purity and yield.For the first time, this study proved the principle that a BES-driven bioconversion of glucose can be achieved for a wild-type obligate aerobe. This non-growth bioconversion was in high yields, high purity and also could deliver the necessary metabolic energy for cell maintenance. By combining this approach with metabolic engineering strategies, this could prove to be a powerful new way to produce bio-chemicals and fuels from renewables in both high yield and high purity.

Medium chain carboxylic acids, such as caproic acid, are conventionally produced from food materials. Caproic acid can be produced through fermentation by the reverse β-oxidation of lactic acid, generated from low value lignocellulosic biomass. In situ extraction of caproic acid can be achieved by membrane electrolysis coupled to the fermentation process, allowing recovery by phase separation.Grass was fermented to lactic acid in a leach-bed-type reactor, which was then further converted to caproic acid in a secondary fermenter. The lactic acid concentration was 9.36 ± 0.95 g L-1 over a 33-day semi-continuous operation, and converted to caproic acid at pH 5.5-6.2, with a concentration of 4.09 ± 0.54 g L-1 during stable production. The caproic acid product stream was extracted in its anionic form, concentrated and converted to caproic acid by membrane electrolysis, resulting in a >70 wt% purity solution. In a parallel test exploring the upper limits of production rate through cell retention, we achieved the highest reported caproic acid production rate to date from a lignocellulosic biomass (grass, via a coupled process), at 0.99 ± 0.02 g L-1 h-1. The fermenting microbiome (mainly consisting of Clostridium IV and Lactobacillus) was capable of producing a maximum caproic acid concentration of 10.92 ± 0.62 g L-1 at pH 5.5, at the border of maximum solubility of protonated caproic acid.Grass can be utilized as a substrate to produce caproic acid. The biological intermediary steps were enhanced by separating the steps to focus on the lactic acid intermediary. Notably, the pipeline was almost completely powered through electrical inputs, and thus could potentially be driven from sustainable energy without need for chemical input.Graphical abstractMicrobial and electrochemical production of lactic acid, caproic acid and decane from grass.

Microbial electrochemistry has from the onset been recognized for its sensing potential due to the microbial ability to enhance signals through metabolic cascades, its relative selectivity toward substrates, and the higher stability conferred by the microbial ability to self-replicate. The greatest challenge has been to achieve stable and efficient transduction between a microorganism and an electrode surface. Over the past decades, a new kind of microbial architecture has been observed to spontaneously develop on polarized electrodes: the electroactive biofilm (EAB). The EAB conducts electrons over long distances and performs quasi-reversible electron transfer on conventional electrode surfaces. It also possesses self-regenerative properties. In only a few years, EABs have inspired considerable research interest for use as biosensors for environmental or bioprocess monitoring. Multiple challenges still need to be overcome before implementation at larger scale of this new kind of biosensors can be realized. This perspective first introduces the specific characteristics of the EAB with respect to other electrochemical biosensors. It summarizes the sensing applications currently proposed for EABs, stresses their limitations, and suggests strategies toward potential solutions. Conceptual prospects to engineer EABs for sensing purposes are also discussed.

ABSTRACT Hydrocarbons released during oil spills are persistent in marine sediments due to the absence of suitable electron acceptors below the oxic zone. Here, we investigated an alternative bioremediation strategy to remove toluene, a model monoaromatic hydrocarbon, using a bioanode. Bioelectrochemical reactors were inoculated with sediment collected from a hydrocarbon-contaminated marine site, and anodes were polarized at 0 mV and +300 mV (versus an Ag/AgCl [3 M KCl] reference electrode). The degradation of toluene was directly linked to current generation of up to 301 mA m −2 and 431 mA m −2 for the bioanodes polarized at 0 mV and +300 mV, respectively. Peak currents decreased over time even after periodic spiking with toluene. The monitoring of sulfate concentrations during bioelectrochemical experiments suggested that sulfur metabolism was involved in toluene degradation at bioanodes. 16S rRNA gene-based Illumina sequencing of the bulk anolyte and anode samples revealed enrichment with electrocatalytically active microorganisms, toluene degraders, and sulfate-reducing microorganisms. Quantitative PCR targeting the α-subunit of the dissimilatory sulfite reductase (encoded by dsrA ) and the α-subunit of the benzylsuccinate synthase (encoded by bssA ) confirmed these findings. In particular, members of the family Desulfobulbaceae were enriched concomitantly with current production and toluene degradation. Based on these observations, we propose two mechanisms for bioelectrochemical toluene degradation: (i) direct electron transfer to the anode and/or (ii) sulfide-mediated electron transfer.

A microbial community is engaged in a complex economy of cooperation and competition for carbon and energy. In engineered systems such as anaerobic digestion and fermentation, these relationships are exploited for conversion of a broad range of substrates into products, such as biogas, ethanol, and carboxylic acids. Medium chain fatty acids (MCFAs), for example, hexanoic acid, are valuable, energy dense microbial fermentation products, however, MCFA tend to exhibit microbial toxicity to a broad range of microorganisms at low concentrations. Here, we operated continuous mixed population MCFA fermentations on biorefinery thin stillage to investigate the community response associated with the production and toxicity of MCFA. In this study, an uncultured species from the Clostridium group IV (related to Clostridium sp. BS-1) became enriched in two independent reactors that produced hexanoic acid (up to 8.1 g L-1), octanoic acid (up to 3.2 g L-1), and trace concentrations of decanoic acid. Decanoic acid is reported here for the first time as a possible product of a Clostridium group IV species. Other significant species in the community, Lactobacillus spp. and Acetobacterium sp., generate intermediates in MCFA production, and their collapse in relative abundance resulted in an overall production decrease. A strong correlation was present between the community composition and both the hexanoic acid concentration (p = 0.026) and total volatile fatty acid concentration (p = 0.003). MCFA suppressed species related to Clostridium sp. CPB-6 and Lactobacillus spp. to a greater extent than others. The proportion of the species related to Clostridium sp. BS-1 over Clostridium sp. CPB-6 had a strong correlation with the concentration of octanoic acid (p = 0.003). The dominance of this species and the increase in MCFA resulted in an overall toxic effect on the mixed community, most significantly on the Lactobacillus spp., which resulted in a decrease in total hexanoic acid concentration to 32 ± 2% below the steady-state average. As opposed to the current view of MCFA toxicity broadly leading to production collapse, this study demonstrates that varied tolerance to MCFA within the community can lead to the dominance of some species and the suppression of others, which can result in a decreased productivity of the fermentation.

Lithium is today an essential raw material for renewable energy technologies and electric mobility. Continental brines as present in the Lithium Triangle are the most abundant and the easiest to exploit lithium sources. Lithium is present in diluted concentrations together with different ions, and it is imperative to fully remove both magnesium and calcium before lithium carbonate can be precipitated. Here we use membrane electrolysis as a novel method to generate hydroxyl groups in situ in a two-chamber electrochemical cell with a side crystallizer, omitting the need for chemical addition and not leading to substantial loss of lithium rich brine. Batch electrolysis experiments fully removed more than 99.99% of both Mg2+ and Ca2+ for three different native South-American brines treated at current densities ranging from 27 to 350 A m−2 (final concentrations were below ICP detection limit: < 0.05 mg L−1). For a brine containing 3090 mg L−1 of Mg2+ and 685 mg L−1 of Ca2+, 62 kWh m−3 are needed for the full removal of both cations when a current density of 223 A m−2 is employed. Most importantly, the Li+ concentration in the brine is not affected. The removed cations are precipitated as Mg(OH)2 and Ca(OH)2. Our process has the potential to simultaneously recover lithium, magnesium, and calcium compounds, minimizing waste production.

Disc shaped microbial aggregates enriched in Ruminococcaceae and lactic acid bacteria produced caproic acid from solid-free thin stillage.

Resource recovery from source-separated urine can shorten nutrient cycles on Earth and is essential in regenerative life support systems for deep-space exploration. In this study, a robust two-stage, energy-efficient, gravity-independent urine treatment system was developed to transform fresh real human urine into a stable nutrient solution. In the first stage, up to 85% of the COD was removed in a microbial electrolysis cell (MEC), converting part of the energy in organic compounds (27–46%) into hydrogen gas and enabling full nitrogen recovery by preventing nitrogen losses through denitrification in the second stage. Besides COD removal, all urea was hydrolysed in the MEC, resulting in a stream rich in ammoniacal nitrogen and alkalinity, and low in COD. This stream was fed into a membrane-aerated biofilm reactor (MABR) in order to convert the volatile and toxic ammoniacal nitrogen to non-volatile nitrate by nitrification. Bio-electrochemical pre-treatment allowed to recover all nitrogen as nitrate in the MABR at a bulk-phase dissolved oxygen level below 0.1 mg O2 L−1. In contrast, feeding the MABR directly with raw urine (omitting the first stage), at the same nitrogen loading rate, resulted in nitrogen loss (18%) due to denitrification. The MEC and MABR were characterised by very distinct and diverse microbial communities. While (strictly) anaerobic genera, such as Geobacter (electroactive bacteria), Thiopseudomonas, a Lentimicrobiaceae member, Alcaligenes and Proteiniphilum prevailed in the MEC, the MABR was dominated by aerobic genera, including Nitrosomonas (a known ammonium oxidiser), Moheibacter and Gordonia. The two-stage approach yielded a stable nitrate-rich, COD-low nutrient solution, suitable for plant and microalgae cultivation.

Precipitation of arsenic as As2S3 produces little waste sludge, has the potential for low chemical consumption and for selective metal(loid) removal. In this study, arsenic removal from acidic (pH 2), metallurgical wastewater was tested in industrially relevant conditions. Sulfides added at a S:As molar ratio of 2.5 and 5 resulted in removal of 99% and 84% of As(III) and As(V). Precipitation of As2S3 from the As(III) and industrial wastewater containing 17% As(V) was nearly instantaneous. For the synthetic As(V) solution, reduction to As(III) was the rate limiting step. At a S:As ratio of 20 and an observed removal rate (k2 = 4.8 (mol L−1) h−1), two hours were required to remove of 93% of arsenic from a 1 g As L−1 solution. In the case of As(V) in industrial samples this time lag was not observed, showing that components in the industrial wastewater affected the removal and reduction of arsenate. Speciation also affected flocculation and coagulation characteristics of As2S3 particles: As(V) reduction resulted in poor coagulation and flocculation. Selective precipitation of arsenic was possible, but depended on speciation, S:As ratio and other metals present.