Phototransformation of perfluorooctane sulfonamide on natural clay minerals: A likely source of short chain perfluorocarboxylic acids.

• Perfluorooctane sulfonamide can transform to perfluocarboxylic acids under sunlight. • Clay mineral can promote the transformation of perfluorooctane sulfonamide. • Water-montmorillonite interface can generate superoxide anion and hydroxyl radical. In this study, a new phototransformation pathway for perfluorooctane sulfonamide (FOSA) and underlying degradation mechanisms are described. Phototransformation of FOSA in a natural clay mineral (montmorillonite) suspension was compared to that in an aqueous solution. Results showed that the presence of montmorillonite can significantly promote the transformation of FOSA to perfluocarboxylic acids (increasing rate). The phototransformation reaction was found to be initiated by the activation of adsorbed oxygen molecules on the surface of montmorillonite, which generate superoxide anion and hydroxyl radicals. Hydroxyl radicals can then attack FOSA adsorbed onto the surface of montmorillonite, promoting the transformation process. In this reaction, clay minerals played a dual role: providing hydroxyl radicals and concentrating FOSA on their surfaces. This helped to promote the contact and reaction between FOSA and hydroxyl radicals. This study provides the first evidence that heterogeneous oxidation of FOSA at the surface of natural clay minerals may act as an important source of perfluocarboxylic acids (PFCAs), especially short chain PFCAs (i.e. trifluoroacetic acid, TFA). [ABSTRACT FROM AUTHOR]