Tetrachloroethane (TeCA) removal through sequential graphite-mixed metal oxide electrodes in a bioelectrochemical reactor

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

Evaluation of a bioelectrochemical reductive/oxidative sequential process for chlorinated aliphatic hydrocarbons (CAHs) removal from a real contaminated groundwater

In the present study, the sequential reductive/oxidative bioelectrochemical process has been tested with real groundwater from a contaminated site in Northern Italy for chlorinated aliphatic hydrocarbons (CAHs) removal. The sequential system was developed by connecting in series two membrane-less microbial electrolysis cells (MECs) equipped with an internal graphite counter electrode. The first MEC aimed at the CAHs reductive dechlorination (RD) and was constituted of a granular graphite working electrode. In the second MEC, a mixed metal oxide working electrode stimulated the oxidative dechlorination of the low chlorinated RD's by-products through oxygen production. The sequential process allowed complete mineralization of the CAHs contained in the real groundwater. A complete reduction of the perchloroethylene into vinyl chloride (VC) was observed in the first MEC polarized at −450 mV vs SHE, while the resulting VC was oxidized with a 92 ± 2 % efficiency in the second MEC due to the HRT increment from 0.7 to 1.7 days. Biomarkers of the reductive (Dehalococcoides mccartyi 16S rRNA and reductive dehalogenase genes) and oxidative (etnE, etnC genes) dechlorination have been monitored in the two MECs along with the ecotoxicity tests. Overall, they provide information on the efficiency of the applied technology and allow to assess the potential adverse effects. According to the Tetrahymena pyriformis reproduction inhibition test and Panagrellus redivivus mortality tests, showed a significant ecotoxicity reduction with respect its initial inhibitory effect at the tested concentrations