As pollution becomes one of the biggest environmental challenges of the twenty-first century, pollution of water threatens the very existence of humanity, making immediate action a priority. The most persistent and hazardous pollutants come from industrial and agricultural activities; therefore, effective treatment of this wastewater prior to discharge into the natural environment is the solution. Advanced oxidation processes (AOPs) have caused increased interest due to their ability to degrade hazardous substances in contrast to other methods, which mainly only transfer pollution from wastewater to sludge, a membrane filter, or an adsorbent. Among a great variety of different AOPs, a group of electrochemical advanced oxidation processes (EAOPs), including electro-Fenton, is emerging as an environmental-friendly and effective treatment process for the destruction of persistent hazardous contaminants. The only concern that slows down a large-scale implementation is energy consumption and related investment and operational costs. A combination of EAOPs with biological treatment is an interesting solution. In such a synergetic way, removal efficiency is maximized, while minimizing operational costs. The goal of this review is to present cutting-edge research for treatment of three common and problematic pollutants and effluents: dyes and textile wastewater, olive processing wastewater, and pharmaceuticals and hospital wastewater. Each of these types is regarded in terms of recent scientific research on individual electrochemical, individual biological and a combined synergetic treatment.

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Electro-Fenton (EF), an advanced oxidation process, can be combined with a biological process for efficient treatment of wastewater containing refractory pollutants such as pharmaceuticals. In this study, a biological process was implemented in a sequencing batch reactor (SBR), which was either preceded or followed by EF treatment. The main goal was to evaluate the potential of two sequences of a combined electrochemical-biological process: EF/SBR and SBR/EF for the treatment of real wastewater spiked with 0.1 mM of caffeine and 5-fluorouracil. The biological removal of COD and pharmaceuticals was improved by extending the acclimation time and increasing concentration of biomass in the SBR. Hardly biodegradable caffeine and COD were completely removed during the EF post-treatment (SBR/EF). During the EF/SBR sequence, complete removal of pharmaceuticals was achieved by EF within 30 min at applied current 800 mA. With a current of 500 and 800 mA, the initially very low BOD/COD ratio increased up to 0.38 and 0.58, respectively, after 30 min. The efficiency of the biological post-treatment was influenced by the biodegradability enhancement after EF pre-treatment. The choice of an adequate sequence of such a combined process is significantly related to the wastewater characteristics as well as the treatment objectives.