Natural Porphyrins Accelerating the Phototransformation of Benzo[a]pyrene in Water

Phototransformation is one of the most important transformation pathways of organic contaminants in the water environment. However, how active compounds enable and accelerate the phototransformation of organic pollutants remains to be elucidated. In this study, the phototransformation of benzo­[a]­pyrene (BaP, the first class “human carcinogens”) by various natural porphyrins under solar irradiation was investigated, including chlorophyll a, sodium copper chlorophyllin, hematin, cobalamin, and pheophorbide a. Transformation efficiency of BaP varied considerably with chemical stabilities of the porphyrins. Porphyrins with a lower stability displayed higher BaP transformation efficiencies. BaP transformation had a significant positive correlation with the production of singlet oxygen. Identical phototransformation products of BaP were observed for all investigated porphyrins, and the main products were identified as BaP-quinones, including BaP-1,6-dione, BaP-3,6-dione, and BaP-6,12-dione. The mechanism of natural porphyrins accelerating the BaP phototransformation in water was proposed to proceed via the photocatalytic generation of singlet oxygen resulting in the transformation of BaP to quinones.