Humidity induces the formation of radicals and enhances photodegradation of chlorinated-PAHs on Fe(III)-montmorillonite

Chlorinated-PAHs (ClPAHs) are widely detected in the soil surface and atmospheric particles. However, the underlying mechanisms of their photodegradation are not well understood. In the present study, the formation of radicals on ClPAHs-contaminated clay minerals was quantitatively monitored via electron paramagnetic resonance (EPR) spectroscopy, and the impact of relative humidity (RH) was systematically explored. ClPAHs removal (> 75%) was attributed to electron transfer and •OH attack. The degradation easiness of ClPAHs follows: 2-ClNAP >2-ClANT >9-ClPHE >1-ClPYR. Light irradiation significantly improved the generation of reactive oxygen species (ROS, such as •OH and •O2−), and further generate a series of hydroxylated products of ClPAHs. Persistent free radicals (PFRs) were only detected on clay minerals contaminated with 2-ClANT and 1-ClPYR. RH 10–80%, the concentration of •OH and •O2− increased by 1.07 and 62.79 times respectively, which facilitated transformation of PFRs and ClPAHs degradation. The results of quantum chemical calculations indicate that the initial reaction of ClPAHs photodegradation is mediated by the substitution of •OH for chlorine groups. The present work implies that higher humidity may decrease the generation of PFRs on clay minerals and help mitigate the threats of PFRs and ClPAHs to human health. [Display omitted] ●ClPAHs were effectively photodegradation on Fe(III)-montmorillonite.●The photodegradation of ClPAHs followed: 2-ClNAP >2-ClANT >9-ClPHE >1-ClPYR.●Humidity facilitated the transformation of persistent free radicals (PFRs).●•OH substitution of chlorine groups mediated the photodegradation of ClPAHs.