An innovative bioelectrochemical reductive/oxidative sequential process was developed and tested on a laboratory scale to obtain the complete mineralization of perchloroethylene (PCE) in a synthetic medium. The sequential bioelectrochemical process consisted of two separate tubular bioelectrochemical reactors that adopted a novel reactor configuration, avoiding the use of an ion exchange membrane to separate the anodic and cathodic chamber and reducing the cost of the reactor. In the reductive reactor, a dechlorinating mixed inoculum received reducing power to perform the reductive dechlorination of perchloroethylene (PCE) through a cathode chamber, while the less chlorinated daughter products were removed in the oxidative reactor, which supported an aerobic dechlorinating culture through in situ electrochemical oxygen evolution. Preliminary fluid dynamics and electrochemical tests were performed to characterize both the reductive and oxidative reactors, which were electrically independent of each other, with each having its own counterelectrode. The first continuous-flow potentiostatic run with the reductive reactor (polarized at −450 mV vs SHE) resulted in obtaining 100% ± 1% removal efficiency of the influent PCE, while the oxidative reactor (polarized at +1.4 V vs SHE) oxidized the vinyl chloride and ethylene from the reductive reactor, with removal efficiencies of 100% ± 2% and 92% ± 1%, respectively.

Groundwater remediation is one of the main objectives to minimize environmental impacts and health risks. Chlorinated aliphatic hydrocarbons contamination is prevalent and presents particularly challenging scenarios to manage with a single strategy. Different technologies can manage contamination sources and plumes, although they are usually energy-intensive processes. Interesting alternatives involve in-situ bioremediation strategies, which allow the chlorinated contaminant to be converted into non-toxic compounds by indigenous microbial activity. Despite several advantages offered by the bioremediation approaches, some limitations, like the relatively low reaction rates and the difficulty in the management and control of the microbial activity, can affect the effectiveness of a bioremediation approach. However, those issues can be addressed through coupling different strategies to increase the efficiency of the bioremediation strategy. This mini review describes different strategies to induce the reduction dechlorination reaction by the utilization of innovative strategies, which include the increase or the reduction of contaminant mobility as well as the use of innovative strategies of the reductive power supply. Subsequently, three future approaches for a greener and more sustainable intervention are proposed. In particular, two bio-based materials from renewable resources are intended as alternative, long-lasting electron-donor sources (e.g., polyhydroxyalkanoates from mixed microbial cultures) and a low-cost adsorbent (e.g., biochar from bio-waste). Finally, attention is drawn to novel bio-electrochemical systems that use electric current to stimulate biological reactions.

Electro-bioremediation offers a promising approach for eliminating persistent pollutants from groundwater since allows the stimulation of biological dechlorinating activity, utilizing renewable electricity for process operation and avoiding the injection of chemicals into aquifers. In this study, a two-chamber microbial electrolysis cell has been utilized to achieve both reductive and oxidative degradation of tetrachloroethane (TeCA). By polarizing the graphite granules cathodic chamber at −650 mV vs the standard hydrogen electrode and employing a mixed metal oxide (MMO) counter electrode for oxygen production, the reductive and oxidative environment necessary for TeCA removal has been established. Continuous experiments were conducted using two feeding solutions: an optimized mineral medium for dechlorinating microorganisms, and synthetic groundwater containing sulphate and nitrate anions to investigate potential side reactions. The bioelectrochemical process efficiently reduced TeCA to a mixture of trans-dichloroethylene, vinyl chloride, and ethylene, which were subsequently oxidized in the anodic chamber with removal efficiencies of 37 ± 2%, 100 ± 4%, and 100 ± 5%, respectively. The introduction of synthetic groundwater with nitrate and sulphate stimulated reductions in these ions in the cathodic chamber, leading to a 17% decrease in the reductive dechlorination rate and the appearance of other chlorinated by-products, including cis-dichloroethylene and 1,2-dichloroethane (1,2-DCA), in the cathode effluent. Notably, despite the lower reductive dechlorination rate during synthetic groundwater operation, aerobic dechlorinating microorganisms within the anodic chamber completely removed VC and 1,2-DCA. This study represents the first demonstration of a sequential reductive and oxidative bioelectrochemical process for TeCA mineralization in a synthetic solution simulating contaminated groundwater.