The exposed hematite surface and the generation of environmentally persistent free radicals during catechol degradation

Abstract

Environmentally persistent free radicals (EPFRs) have drawn increasing attention. It is reported that EPFR formation is dependent on the presence of transition metals; however the size of the metal particles is ignored. In this study, we hypothesized that transition metals in smaller particle sizes could more efficiently promote the generation of EPFRs and thus have higher risks. Nanosized hematite (nanoHMT) and microsized hematite (microHMT) were studied and compared. We monitored the degradation of catechol and the generation of EPFRs under both dark and ultraviolet light conditions. Catechol degradation was inhibited in the presence of hematite in the dark, with more significant inhibition by nanoHMT. However, under ultraviolet light, catechol degradation was promoted by hematite, with more significant promotion by nanoHMT. The yield of free radicals in the nanoHMT system was always higher than that in the microHMT system. More dimers were detected in the nanoHMT system, which may have played an important role in stabilizing free radicals. More trivalent Fe was converted to divalent Fe in the nanoHMT system than in the microHMT system. The relatively more active sites for the catechol interaction promoted EPFR generation. These results highlighted that size-dependent reactions should be well considered when predicting the environmental behavior and risks of organic contaminants.