Photo-Fenton oxidation of cylindrospermopsin at neutral pH with LEDs

Cylindrospermopsin (CYN) is a potent cyanobacterial toxin found in freshwaters worldwide. In this work, the feasibility of the photo-Fenton process under neutral pH using light emitting diodes as irradiation source for the removal of this hazardous cyanotoxin from freshwater was investigated. The impact of the kind of iron chelating agent (ethylenediamine-N, N'-disuccinic acid vs. ethylenedinitrilotetraacetic acid) as well as the effect of the main operating conditions viz. H₂O₂ dose, Fe(III) load, initial CYN concentration, and Fe(III):EDDS molar ratio on the performance of the process was systematically evaluated. EDDS was selected as the most appropriate iron chelating agent considering the kinetics of the process and the environmental impact (Vibrio fischeri and Artemia salina). Under optimized conditions ([H₂O₂] = 30 mg L^-1; [Fe(III)] = 5 mg L^-1; Fe(III):ligand = 1:0.5 (molar ratio)), complete removal of CYN was achieved in 15-min reaction time. Furthermore, the catalytic system showed to be effective in real water matrices (river and reservoir waters) spiked with CYN. Although the presence of inorganic ions (mainly HCO₃^-/CO₃^2-) and dissolved organic carbon decreased the oxidation rate of CYN due to scavenging reactions and iron coordination, respectively, complete elimination of the cyanotoxin was achieved in all cases. The fate of EDDS along the process was also evaluated to demonstrate that the catalytic system investigated, apart from its effectiveness, warrants the complete absence of residues after reaction. Therefore, the proposed system constitutes a promising method for cyanotoxin treatment either as a drinking water treatment step in conventional plants or as a potential remediation strategy in the natural environment.