Groundwater is the environmental matrix that is most frequently affected by anthropogenic hexavalent chromium contamination. Due to its carcinogenicity, Cr(VI) has to be removed, using environmental-friendly and economically sustainable remediation technologies. BioElectrochemical Systems (BESs), applied to bioremediation, thereby offering a promising alternative to traditional bioremediation techniques, without affecting the natural groundwater conditions. Some bacterial families are capable of oxidizing and/or reducing a solid electrode obtaining an energetic advantage for their own growth. In the present study, we assessed the possibility of stimulating bioelectrochemical reduction of Cr(VI) in a dual-chamber polarized system using an electrode as the sole energy source. To develop an electroactive microbial community three electrodes were, at first, inserted into the anodic compartment of a dual-chamber microbial fuel cell, and inoculated with sludge from an anaerobic digester. After a period of acclimation, one electrode was transferred into a polarized system and it was fixed at −0.3 V (versus standard hydrogen electrode, SHE), to promote the reduction of 1000 µg Cr(VI) L⁻¹. A second electrode, served for the set-up of an open circuit control, operated in parallel. Cr(VI) dissolved concentration was analysed at the initial, during the experiment and final time by spectrophotometric method. Initial and final microbial characterization of the communities enriched in polarized system and open circuit control was performed by 16S rRNA gene sequencing. The bioelectrode set at −0.3 V showed high Cr(VI) removal efficiency (up to 93%) and about 150 µg L⁻¹ day⁻¹ removal rate. Similar efficiency was observed in the open circuit (OC) even at about half rate. Whereas, purely electrochemical reduction, limited to 35%, due to neutral operating conditions. These results suggest that bioelectrochemical Cr(VI) removal by polarized electrode offers a promising new and sustainable approach to the treatment of groundwater Cr(VI) plumes, deserving further research.

Bioelectrochemical remediation of hydrocarbons is a technology that exploits the ability of specific microorganisms to use as electron acceptor an electrode, thus potentially lowering the operational costs related to classical bioremediation. Several well-characterized hydrocarbonoclastic strains might be electroactive, thus their biodegradation performances in Bioelectrochemical Systems should be studied. Cupriavidus metallidurans CH34 is a model metal-resistant strain whose capacity to degrade benzene aerobically has recently been described. In this study, toluene degradation under anaerobic conditions and the exoelectrogenic capacity of Cupriavidus metallidurans CH34 were determined. Strain CH34 was grown anaerobically with toluene as sole carbon source in sealed serum bottles and then inoculated in a Microbial Electrolysis Cell (MEC) to assess its exoelectrogenic capacity. It was demonstrated for the first time that strain CH34 is able to degrade toluene under nitrate-reducing conditions (up to 45 mg_toluene/L were removed within 17 days, corresponding to 73% of toluene amended). Nitrate consumption and cellular growth were observed during toluene removal. In the MEC, toluene degradation was linked to current production, showing current peaks after every toluene addition (maximum current density 48 mA/m²). Coulombic efficiency of the toluene biodegradation process increased with time, from 11% (first batch cycle), up to 77% (last batch cycle).

Microbial electrochemical systems (MES) represent an innovative reagent-free technology for in situ remediation of groundwater contaminated by petroleum hydrocarbons. Here we describe the long-term (>160 days) anaerobic treatment of synthetic groundwater containing toluene (25 mg L⁻¹) in a novel laboratory-scale, continuous-flow bioelectrochemical reactor, termed the “bioelectric well”. Under optimal operating conditions (i.e., anode potential potentiostatically controlled at +0.2 V vs. SHE and recycle flow-rate set at 75 mL min⁻¹), the observed electrogenic toluene oxidation rate was 67.2 ± 5.7 mg L d⁻¹, a value which is among the highest reported in the literature for laboratory-scale anaerobic treatment systems. Correspondingly, electric current was 5.1 ± 0.1 mA and the Coulombic efficiency (i.e., the yield of toluene conversion into electric current) was 79 ± 7%. Electrogenic toluene oxidation was most likely catalyzed by Geobacter species, which were found to dominate the surface of the graphite anode. The combined application of GC-MS (for detection and identification of metabolites) and qPCR (for quantification of functional genes) revealed that toluene degradation was initiated by fumarate addition, an activation pathway that is widely distributed among anaerobic hydrocarbon-degrading microorganisms. Collectively, the results of this study indicate that the bioelectric well holds remarkable potential for in situ treatment of groundwater contaminated by petroleum hydrocarbons.

Bioelectrochemical systems (BESs) exploit the interaction between microbes and electrodes. A field of application thereof is bioelectrochemical remediation, an effective strategy in environments where the absence of suitable electron acceptors limits classic bioremediation approaches. Understanding the microbial community structure and genetic potential of anode biofilms is of great interest to interpret the mechanisms occurring in BESs. In this study, by using a whole metagenome sequencing approach, taxonomic and functional diversity patterns in the inoculum and on the anodes of three continuous-flow BES for the removal of phenol, toluene, and BTEX were obtained. The genus Geobacter was highly enriched on the anodes and two reconstructed genomes were taxonomically related to the Geobacteraceae family. To functionally characterize the microbial community, the genes coding for the anaerobic degradation of toluene, ethylbenzene, and phenol were selected as genetic markers for the anaerobic degradation of the pollutants. The genes related with direct extracellular electron transfer (EET) were also analyzed. The inoculum carried the genetic baggage for the degradation of aromatics but lacked the capacity of EET while anodic bacterial communities were able to pursue both processes. The metagenomic approach provided useful insights into the ecology and complex functions within hydrocarbon-degrading electrogenic biofilms.