Decomplexation of Cu(II)-natural organic matter complex by non-thermal plasma oxidation: Process and mechanisms

Heavy metals and natural organic matters (NOM) form very stable heavy metal-NOM complexes in aqueous, facilitating the migration of heavy metals and enhancing their potential risks. In this study, non-thermal plasma oxidation was attempted to destroy the heavy metal-NOM complexes, with Cu-humate (Cu-HA) as a model. The decomplexation efficiency reached 86.1 % within 50 min of plasma oxidation at 16 kV. The generated reactive species by the non-thermal plasma, including O₂^-, ¹O₂, OH, attacked the carboxyl and hydroxyl functional groups of HA, leading to cleavage of the Cu-O bonds, decomplexation of Cu-HA, and release of free Cu(II). Meanwhile, a variety of small molecular intermediates, including phenols, benzoic acids, esters, amines, ketones, acetic acid, formic acid, and oxalic acid, were generated due to attack by the oxidative species on the aromatic moiety and double bonds in Cu-HA. As a consequence of decomplexation, the residual toxicity of Cu-HA to Scenedesmus obliquus was distinctly reduced. This study provides a potential technique to decomplex heavy metal-NOM complexes, and reduces their toxicity to typical Scenedesmus obliquus.