Degradation of widespread cyanotoxins with high impact in drinking water (microcystins, cylindrospermopsin, anatoxin-a and saxitoxin) by CWPO

Abstract

The occurrence of harmful cyanobacterial blooms has unabated increased over the last few decades, posing a significant risk for public health. In this work, we investigate the feasibility of catalytic wet peroxide oxidation (CWPO) promoted by modified natural magnetite (Fe₃O₄-R400/H₂O₂), as an inexpensive, simple-operation and environmentally-friendly process for the removal of the cyanotoxins that show the major impact on drinking water: microcystins (MC-LR and MC-RR), cylindrospermopsin (CYN), anatoxin-a (ATX) and saxitoxin (STX). The performance of the system was evaluated under ambient conditions and circumneutral pH (pH₀ = 5) using relevant cyanotoxin concentrations (100-500 μg L^-1). The nature of the cyanotoxins determined their reactivity towards CWPO, which decreased in the following order: MC-RR > CYN > MC-LR ≫ ATX > STX. In this sense, microcystins and CYN were completely removed in short reaction times (1-1.5 h) with a low catalyst concentration (0.2 g L^-1) and the stoichiometric amount of H₂O₂ (2-2.6 mg L^-1), while only 60-80% conversion was achieved with ATX and STX in 5 h. In these cases, an intensification of the operating conditions (1 g L^-1 catalyst and up to 30 mg H₂O₂ L^-1) was required to remove both toxins in 1 h. The impact of the main components of freshwaters i.e. natural organic matter (NOM) and several inorganic ions (HCO₃^-, HPO₄^2-, SO₄^2-) on the performance of the process was also investigated. Although the former led to a partial inhibition of the reaction due to HO· scavenging and catalyst coating, the latter did not show any remarkably effect, and the versatility of the process was finally confirmed in a real surface water. To further demonstrate the effectiveness of the catalytic system, the toxicity of both the initial cyanotoxins and the resulting CWPO effluents was measured with the brine shrimp Artemia salina. Remarkably, all CWPO effluents were non-toxic at the end of the treatment.

Keywords: Anatoxin-a; CWPO; Cyanotoxin; Cylindrospermopsin; Microcystin; Saxitoxin.