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.

Chromium is one of the most frequently used metal contaminants. Its hexavalent form Cr(VI), which is exploited in many industrial activities, is highly toxic, is water-soluble in the full pH range, and is a major threat to groundwater resources. Alongside traditional approaches to Cr(VI) treatment based on physical-chemical methods, technologies exploiting the ability of several microorganisms to reduce toxic and mobile Cr(VI) to the less toxic and stable Cr(III) form have been developed to improve the cost-effectiveness and sustainability of remediating hexavalent chromium-contaminated groundwater. Bioelectrochemical systems (BESs), principally investigated for wastewater treatment, may represent an innovative option for groundwater remediation. By using electrodes as virtually inexhaustible electron donors and acceptors to promote microbial oxidation-reduction reactions, in in situ remediation, BESs may offer the advantage of limited energy and chemicals requirements in comparison to other bioremediation technologies, which rely on external supplies of limiting inorganic nutrients and electron acceptors or donors to ensure proper conditions for microbial activity. Electron transfer is continuously promoted/controlled in terms of current or voltage application between the electrodes, close to which electrochemically active microorganisms are located. Therefore, this enhances the options of process real-time monitoring and control, which are often limited in in situ treatment schemes. This paper reviews research with BESs for treating chromium-contaminated wastewater, by focusing on the perspectives for Cr(VI) bioelectrochemical remediation and open research issues.

Sites contaminated by hexavalent chromium raise concerns relating to the toxicity of the pollutant, as well as for the increased solubility of its compounds, which helps it to seep into aquifers. Chemical and biological in situ treatment technologies, with good potential in terms of environmental sustainability, have recently been designed and implemented on a wide scale. A useful support tool is shown in the manuscript in the preliminary phase of assessing possible technologies applicable according to the site-specific characteristics of sites. The actual efficacy of the technologies identified should nevertheless be verified in laboratory trials and pilot tests.