Does pre-enrichment of anodes with acetate to select for Geobacter spp. enhance performance of microbial fuel cells when switched to more complex substrates?

Many factors affect the performance of microbial fuel cells (MFCs). Considerable attention has been given to the impact of cell configuration and materials on MFC performance. Much less work has been done on the impact of the anode microbiota, particularly in the context of using complex substrates as fuel. One strategy to improve MFC performance on complex substrates such as wastewater, is to pre-enrich the anode with known, efficient electrogens, such as Geobacter spp. The implication of this strategy is that the electrogens are the limiting factor in MFCs fed complex substrates and the organisms feeding the electrogens through hydrolysis and fermentation are not limiting. We conducted a systematic test of this strategy and the assumptions associated with it. Microbial fuel cells were enriched using three different substrates (acetate, synthetic wastewater and real domestic wastewater) and three different inocula (Activated Sludge, Tyne River sediment, effluent from an MFC). Reactors were either enriched on complex substrates from the start or were initially fed acetate to enrich for Geobacter spp. before switching to synthetic or real wastewater. Pre-enrichment on acetate increased the relative abundance of Geobacter spp. in MFCs that were switched to complex substrates compared to MFCs that had been fed the complex substrates from the beginning of the experiment (wastewater-fed MFCs - 21.9 ± 1.7% Geobacter spp.; acetate-enriched MFCs, fed wastewater - 34.9 ± 6.7% Geobacter spp.; Synthetic wastewater fed MFCs - 42.5 ± 3.7% Geobacter spp.; acetate-enriched synthetic wastewater-fed MFCs - 47.3 ± 3.9% Geobacter spp.). However, acetate pre-enrichment did not translate into significant improvements in cell voltage, maximum current density, maximum power density or substrate removal efficiency. Nevertheless, coulombic efficiency (CE) was higher in MFCs pre-enriched on acetate when complex substrates were fed following acetate enrichment (wastewater-fed MFCs - CE = 22.0 ± 6.2%; acetate-enriched MFCs, fed wastewater - CE =58.5 ± 3.5%; Synthetic wastewater fed MFCs - CE = 22.0 ± 3.2%; acetate-enriched synthetic wastewater-fed MFCs - 28.7 ± 4.2%.) The relative abundance of Geobacter ssp. and CE represents the average of the nine replicate reactors inoculated with three different inocula for each substrate. Efforts to improve the performance of anodic microbial communities in MFCs utilizing complex organic substrates should therefore focus on enhancing the activity of organisms driving hydrolysis and fermentation rather the terminal-oxidizing electrogens.

Zinc removal and recovery from industrial wastewater with a microbial fuel cell: Experimental investigation and theoretical prediction.

Microbial fuel cells (MFCs) that simultaneously remove organic contaminants and recovering metals provide a potential route for industry to adopt clean technologies. In this work, two goals were set: to study the feasibility of zinc removal from industrial effluents using MFCs and to understand the removal process by using reaction rate models. The removal of Zn2+ in MFC was over 96% for synthetic and industrial samples with initial Zn2+ concentrations less than 2.0 mM after 22 h of operation. However, only 83 and 42% of the zinc recovered from synthetic and industrial samples, respectively, was attached on the cathode surface of the MFCs. The results marked the domination of electroprecipitation rather than the electrodeposition process in the industrial samples. Energy dispersive X-ray (EDX) analysis showed that the recovered compound contained not only Zn but also O, evidence that Zn(OH)2 could be formed. The removal of Zn2+ in the MFC followed a mechanism where oxygen was reduced to hydroxide before reacting with Zn2+. Nernst equations and rate law expressions were derived to understand the mechanism and used to estimate the Zn2+ concentration and removal efficiency. The zero-, first- and second-order rate equations successfully fitted the data, predicted the final Zn2+ removal efficiency, and suggested that possible mechanistic reactions occurred in the electrolysis cell (direct reduction), MFC (O2 reduction), and control (chemisorption) modes. The half-life, t1/2, of the Zn2+ removal reaction using synthetic and industrial samples was estimated to be 7.0 and 2.7 h, respectively. The t1/2 values of the controls (without the power input from the MFC bioanode) were much slower and were recorded as 21.5 and 7.3 h for synthetic and industrial samples, respectively. The study suggests that MFCs can act as a sustainable and environmentally friendly technology for heavy metal removal without electrical energy input or the addition of chemicals.

Bioelectrochemical treatment and recovery of copper from distillery waste effluents using power and voltage control strategies.

Copper recovery from distillery effluent was studied in a scalable bioelectro-chemical system with approx. 6.8 L total volume. Two control strategies based on the control of power with maximum power point tracking (MPPT) and the application of 0.5 V using an external power supply were used to investigate the resultant modified electroplating characteristics. The reactor system was constructed from two electrically separated, but hydraulically connected cells, to which the MPPT and 0.5 V control strategies were applied. Three experiments were carried out using a relatively high copper concentration i.e. 1000 mg/L followed by a lower concentration i.e. 50 mg/L, with operational run times defined to meet the treatment requirements for distillery effluents considered. Real distillery waste was introduced into the cathode to reduce ionic copper concentrations. This waste was then recirculated to the anode as a feed stock after the copper depletion step, in order to test the bioenergy self-sustainability of the system. Approx. 60-95% copper was recovered in the form of deposits depending on starting concentration. However, the recovery was low when the anode was supplied with copper depleted distillery waste. Through process control (MPPT or 0.5 V applied voltage) the amount and form of the copper recovered could be manipulated.

Cosmic ray radiography of the damaged cores of the Fukushima reactors.

The passage of muons through matter is dominated by the Coulomb interaction with electrons and nuclei. The interaction with the electrons leads to continuous energy loss and stopping of the muons. The interaction with nuclei leads to angle "diffusion." Two muon-imaging methods that use flux attenuation and multiple Coulomb scattering of cosmic-ray muons are being studied as tools for diagnosing the damaged cores of the Fukushima reactors. Here, we compare these two methods. We conclude that the scattering method can provide detailed information about the core. Attenuation has low contrast and little sensitivity to the core.

Collision-induced dissociation of halide ion-arginine complexes: evidence for anion-induced zwitterion formation in gas-phase arginine.

We report the first low-energy collisional-induced dissociation studies of the X(-)·arginine (X(-) = F(-), Cl(-), Br(-), I(-), NO(3)(-), ClO(3)(-)) series of clusters to investigate the novel phenomenom of anion-induced zwitterion formation in a gas-phase amino acid. Fragmentation of the small halide ion clusters (F(-)·arginine and Cl(-)·arginine) is dominated by deprotonation of the arginine, whereas the major fragmentation channel for the largest ion clusters (I(-)·arginine and ClO(3)(-)·arginine) corresponds to simple cluster fission into the ion and neutral molecule. However, the fragmentation profiles of Br(-)·arginine and NO(3)(-)·arginine, display distinctive features that are consistent with the presence of the zwitterionic form of the amino acid in these clusters. The various dissociation pathways have been studied as a function of % collision energy and are discussed in comparison to the fragmentation profiles of protonated and deprotonated arginine. Electronic structure calculations are presented for Br(-)·arginine to support the presence of the zwitterionic amino acid in this complex. The results obtained in this work provide important information on the low-energy potential energy surfaces of these anion-amino acid clusters and reveal the presence of several overlapping surfaces in the low-energy region for the Br(-)·arginine and NO(3)(-)·arginine systems.

Evidence for hydrogen bond network formation in microsolvated clusters of Pt(CN)4(2-): collision induced dissociation studies of Pt(CN)4(2-)·(H2O)(n) n = 1-4, and Pt(CN)4(2-)·(MeCN)(m) m = 1, 2 cluster ions.

Low-energy collision induced dissociation has been used to investigate the structure and stability of microsolvated clusters of the prototypical, aprotic multiply charged anion, Pt(CN)(4)(2-), i.e. Pt(CN)(4)(2-)·(H(2)O)(n) n = 1-4, Pt(CN)(4)(2-)·(MeCN)(m) m =1, 2, and Pt(CN)(4)(2-)·(H(2)O)(3)·MeCN. For all of the systems studied, the lowest energy fragmentation pathway was found to correspond to decay of the cluster with loss of the entire solvent ensemble. No sequential solvent evaporation was observed. These observations suggest that the Pt(CN)(4)(2-) solvent clusters studied here form hydrogen-bonded "surface solvated" structures. Electronic structure calculations are presented to support the experimental results. In addition, the detailed fragmentation patterns observed are interpreted with reference to the differential solvation of the ionic fragmentation and electron detachment potential energy surfaces of the core Pt(CN)(4)(2-) dianion. The results described represent some of the first experiments to probe the microsolvation of this important class of multiply charged anions.