In this work, hydrogen peroxide (H2O2) is produced using an optimized electrochemical cell equipped with a gas diffusion electrode (GDE) as cathode, reaching efficiencies as high as 20.1%, when operating in a single compartment configuration, which increases up to the range 50–60, when a proton exchange membrane is used to separate the anodic and cathodic compartments, pointing out the great significance of the anodic oxidation of H2O2 and the scavenging effects of the oxidants produced on the anode surface. As compared to previous materials tested, the GDE implemented in this cell underwent a more sustainable manufacturing procedure and exhibited an outstanding performance. The H2O2 produced electrochemically is dosed to the real leachate of an industrial dump, strongly polluted with derivatives of lindane. This waste is associated to the operation of a large facility in the seventies and contains different isomers of hexachlorocyclohexane and other chlorinated hydrocarbons, produced during the ageing of the dump. Effects of the addition of iron (II) sulfate salts and irradiation of UVC were also evaluated. All electrochemically-assisted technologies evaluated (named as chemical (EACO), Fenton (EAFO), photolysis (EAPO) and photo-Fenton (EAPFO) oxidations) were able to successfully remove the pollutants, although with important differences in the efficiencies reached. Results demonstrate that EACO, that is, oxidation by molecular H2O2 is the most effective treatment for the treatment of this type of wastes, pointing out that activation of H2O2 to hydroxyl radicals, either by electrochemically assisted Fenton or photolysis is not positive for this waste. As well, among the different pollutants contained in the raw waste, removal of hexachlorocyclohexane (HCHs) and non-chlorinated volatile organic compounds (VOCs) stands out (both groups being the primary species contained in the wastes). These results are very important not only because of the outstanding productions of H2O2 reached with the novel approach of electrochemical cell used, but also because of the implications of the mechanistic understanding of the attack of H2O2 species in the design of a full-scale application to remediate this real important problem.
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