Bioelectrochemical Denitrification for the Treatment of Saltwater Recirculating Aquaculture Streams

Maintaining low concentrations of nitrogen compounds (ammonium, nitrate and nitrite) in recirculating aquaculture waters is extremely important for a larger and healthier fish production, as well as for water discharge purposes. Although ammonium removal from aquaculture streams is usually done within a nitrifying step, nitrate removal via denitrification is still partially limited by the low organic matter availability. Therefore, an easy-to-operate autotrophic denitrifying bioelectrochemical system is herein proposed for the treatment of seawater aquaculture streams. The nitrate-containing synthetic stream flows sequentially through a biological denitrifying cathode (placed at the lower portion of a tubular reactor) and an abiotic anode (generating electrons and oxygen from water splitting, at the upper portion). Experimental results with synthetic seawater showed that the system reached denitrification rates of 0.13 ± 0.01 kg N m–3 day–1, operating with minimum ammonium and nitrite accumulation, as well as minimum chlorine formation in the abiotic anode, despite the high chloride concentration. There results support the technical potential for simultaneous bioelectrochemical denitrification and partial re-oxygenation of aquaculture waters either for recirculation or discharge purposes

Syntrophic Processes Drive the Conversion of Glucose in Microbial Fuel Cell Anodes

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

Electron and Carbon Balances in Microbial Fuel Cells Reveal Temporary Bacterial Storage Behavior During Electricity Generation

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

Oxygen Suppresses Light-Driven Anodic Current Generation by a Mixed Phototrophic Culture

This paper describes the detrimental effect of photosynthetically evolved oxygen on anodic current generation in the presence of riboflavin upon illumination of a mixed phototrophic culture enriched from a freshwater pond at +0.6 V vs standard hydrogen electrode. In the presence of riboflavin, the phototrophic biomass in the anodic compartment produced an electrical current in response to light/dark cycles (12 h/12 h) over 12 months of operation, generating a maximum current density of 17.5 mA.m^–2 during the dark phase, whereas a much lower current of approximately 2 mA.m^–2 was generated during illumination. We found that the low current generation under light exposure was caused by high rates of reoxidation of reduced riboflavin by oxygen produced during photosynthesis. Quantification of biomass by fluorescence in situ hybridization images suggested that green algae were predominant in both the anode-based biofilm (55.1%) and the anolyte suspension (87.9%) with the remaining biovolume accounted for by bacteria. Genus-level sequencing analysis revealed that bacteria were dominated by cyanobacterium <i>Leptolyngbia</i> (∼35%), while the prevailing algae were <i>Dictyosphaerium</i>, <i>Coelastrum</i>, and <i>Auxenochlorella</i>. This study offers a key comprehension of mediator sensitivity to reoxidation by dissolved oxygen for improvement of microbial solar cell performance

Carbon and Electron Fluxes during the Electricity Driven 1,3-Propanediol Biosynthesis from Glycerol

1,3-Propanediol (1,3-PDO) can be produced biologically through glycerol fermentation. While such a process typically involves a pure culture system, particularly for crude glycerol, there would be operational advantages if a mixed population could be used. However, in the latter case the yield is typically low. Here, we use electrical current as the driving force for a mixed population fermenting glycerol in the cathode of a microbial bioelectrochemical system (BES). The carbon and electron flows were monitored by a titration and off-gas analysis (TOGA) sensor, and the syntrophic interactions in the BES were also investigated. Results show that on a carbon yield basis, current enhanced 1,3-PDO production from 24.8% (without current) to 50.1% (with a polarized biocathode at −0.9 V versus standard hydrogen electrode, SHE). Flux analysis indicated that the reductive current can be integrated into glycerol metabolism to enhance 1,3-PDO yield and that glycerol metabolism was redirected from propionate fermentation to 1,3-PDO production. A polarization of −0.6 V (vs SHE) resulted in more fermentative hydrogen production (from 2.7% to 8.0% on electron basis). 1,3-PDO production was also enhanced with hydrogen supply (37.7% on carbon basis), by suppressing hydrogen fermentation. Moreover, interspecies hydrogen transfer encouraged hydrogenotrophic methanogenesis, which was also accelerated by the cathodic polarization

Microbial Electrosynthesis of Isobutyric, Butyric, Caproic Acids, and Corresponding Alcohols from Carbon Dioxide

Microbial electrosynthesis is potentially a sustainable biotechnology for the conversion of the greenhouse gas CO₂ into carboxylic acids, thus far mostly limited to acetic acid (C2). Despite the environmental benefits of recycling CO₂ emissions to counter global warming, bioelectrochemical production of acetate is not very attractive from an economic point of view. Conversely, carboxylates and corresponding alcohols with longer C content not only have a higher economical value as compared to acetate, but they are also relevant platform chemicals and fuels used on a diverse array of industrial applications. Here, we report on a specific mixed reactor microbiome capable of producing a mixture of C4 and C6 carboxylic acids (isobutyric, <i>n</i>-butyric, and <i>n</i>-caproic acids) and their corresponding alcohols (isobutanol, <i>n</i>-butanol, and <i>n</i>-hexanol) using CO₂ as the sole carbon source and reducing power provided by an electrode. Metagenomic analysis supports the hypothesis of a sequential carbon chain elongation process comprised of acetogenesis, solventogenesis, and reverse β-oxidation, and that isobutyric acid is derived from the isomerization of <i>n</i>-butyric acid

Microbial Electrosynthesis of Isobutyric, Butyric, Caproic Acids, and Corresponding Alcohols from Carbon Dioxide

Microbial electrosynthesis is potentially a sustainable biotechnology for the conversion of the greenhouse gas CO₂ into carboxylic acids, thus far mostly limited to acetic acid (C2). Despite the environmental benefits of recycling CO₂ emissions to counter global warming, bioelectrochemical production of acetate is not very attractive from an economic point of view. Conversely, carboxylates and corresponding alcohols with longer C content not only have a higher economical value as compared to acetate, but they are also relevant platform chemicals and fuels used on a diverse array of industrial applications. Here, we report on a specific mixed reactor microbiome capable of producing a mixture of C4 and C6 carboxylic acids (isobutyric, <i>n</i>-butyric, and <i>n</i>-caproic acids) and their corresponding alcohols (isobutanol, <i>n</i>-butanol, and <i>n</i>-hexanol) using CO₂ as the sole carbon source and reducing power provided by an electrode. Metagenomic analysis supports the hypothesis of a sequential carbon chain elongation process comprised of acetogenesis, solventogenesis, and reverse β-oxidation, and that isobutyric acid is derived from the isomerization of <i>n</i>-butyric acid

Effects of Surface Charge and Hydrophobicity on Anodic Biofilm Formation, Community Composition, and Current Generation in Bioelectrochemical Systems

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 <i>Geobacter</i> 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<i>. Geobacter</i>) and more conducive for electroactive biofilm formation

Flame Oxidation of Stainless Steel Felt Enhances Anodic Biofilm Formation and Current Output in Bioelectrochemical Systems

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/cm2, 27.42 mA/cm3) 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

High Acetic Acid Production Rate Obtained by Microbial Electrosynthesis from Carbon Dioxide

High product specificity and production rate are regarded as key success parameters for large-scale applicability of a (bio)­chemical reaction technology. Here, we report a significant performance enhancement in acetate formation from CO₂, reaching comparable productivity levels as in industrial fermentation processes (volumetric production rate and product yield). A biocathode current density of −102 ± 1 A m^–2 and an acetic acid production rate of 685 ± 30 (g m^–2 day^–1) have been achieved in this study. High recoveries of 94 ± 2% of the CO₂ supplied as the sole carbon source and 100 ± 4% of electrons into the final product (acetic acid) were achieved after development of a mature biofilm, reaching an elevated product titer of up to 11 g L^–1. This high product specificity is remarkable for mixed microbial cultures, which would make the product downstream processing easier and the technology more attractive. This performance enhancement was enabled through the combination of a well-acclimatized and enriched microbial culture (very fast start-up after culture transfer), coupled with the use of a newly synthesized electrode material, EPD-3D. The throwing power of the electrophoretic deposition technique, a method suitable for large-scale production, was harnessed to form multiwalled carbon nanotube coatings onto reticulated vitreous carbon to generate a hierarchical porous structure