Microbial electrochemical technologies (MET) rely on the presence of the metabolic activity of electroactive bacteria for the use of solid-state electrodes for oxidizing different kinds of compound that can lead to the synthesis of chemicals, bioremediation of polluted matrices, the treatment of contaminants of interest, as well as the recovery of energy. Keeping these possibilities in mind, there has been growing interest in the use of electrochemical technologies for wastewater treatment, if possible with simultaneous power generation, since the beginning of the present century. In the last few years, there has been growing interest in exploring the possibility of merging MET with constructed wetlands offering a new option of an intensified wetland system that could maintain a high performance with a lower footprint. Based on that interest, this paper explains the general principles of MET, and the different known extracellular electron transfer mechanisms ruling the interaction between electroactive bacteria and potential solid-state electron acceptors. It also looks at the adoption of those principles for the development of MET set-ups for simultaneous wastewater treatment and power generation, and the challenges that the technology faces. Ultimately, the most recent developments in setups that merge MET with constructed wetlands are presented and discussed.

In this work, we present for the first time the concept of integrating microbial electrochemical technologies (MET) with natural wastewater treatment biofilters used in constructed wetlands (CW) to form METlands. In order to validate this technology, three lab-scale horizontal subsurface flow (HSSF) biofilters, two hosting electroconductive materials and one gravel biofilter (control) were operated for 525 days to define the best design and operational conditions to maximize the removal of wastewater pollutants. Organic loading rates tested ranged from 2 to 24 g BOD₅ m⁻² d⁻¹ at hydraulic retention times (HRT) from 4 days to as low as 0.5 day, respectively. The electroconductive biofilter showed the best COD and BOD removal rates per volume of bed, achieving mean values of 213 g COD m⁻³ d⁻¹ and 119 g BOD m⁻³ d⁻¹ at the lowest HRT (0.5 d). Ammonia and total nitrogen maximum removal efficiencies at 3.4 days of HRT were 97 and 69%, respectively, in the electroconductive biofilter. Bacterial communities were studied by 16S rDNA Illumina sequencing with the aim of understanding the role of the electrically conductive material in selecting microbial populations. Deltaproteobacteria (a known electroactive taxon) were enriched in the presence of an electrically conductive bed. Geobacter and Geothrix were the dominant genera in the deeper zone of the electrically conductive bed where oxidation of organic matter occurred. The results suggest that the enhancement in biodegradation rate will significantly reduce the area requirements of classical CW.

Domestic and industrial wastewaters contain organic substrates and nutrients that can be recovered instead of being dissipated by emerging efficient technologies. The aim of this study was to promote bio-hydrogen production and carbon fixation using a mixed culture of purple phototrophic bacteria (PPB) that use infrared radiation in presence or absence of an electrode as electron donor. In order to evaluate the hydrogen production under electrode-free conditions, batch experiments were conducted using different nitrogen (NH₄Cl, Na-glutamate, N₂ gas) and carbon sources (malic-, butyric-, acetic- acids) under various COD:N ratios. Results suggested that the efficiency of PPB to produce biogenic H₂ was highly dependent on the substrates used. The maximum hydrogen production (H_{2_max}, 423 mLH₂/L) and production rate (H_{2_rate}, 2.71 mLH₂/Lh) were achieved using malic acid and Na-glutamate at a COD:N ratio of 100:15. Under these optimum conditions, a significant fixation of nitrogen in form of single-cell proteins (874.4 mg/L) was also detected. Under bio-electrochemical conditions using a H-cell bio-electrochemical device, the PPB were grown planktonic in the bio-cathode chamber with the optimum substrate ratio of malic acid and Na-glutamate. A redox potential of −0.5 V (vs. Ag/AgCl) under bio-electrochemical conditions produced comparable amounts of bio-hydrogen but significantly negligible traces of CO₂ as compared to the biological system (11.8 mLCO₂/L). This suggests that PPB can interact with the cathode to extract electrons for further CO₂ re-fixation (coming from the Krebs cycle) into the Calvin cycle, thereby improving the C usage. It has also been observed during cyclic voltammograms that a redox potential of −0.8 V favors considerably the electrons consumption by the PPB culture, suggesting that the PPB can use these electrons to increase the biohydrogen production. These results are expected to prove the feasibility of stimulating PPB through bio-electrochemical processes in the production of H₂ from wastewater resources, which is a field of special novelty and still unexplored.