%A Hanzhong Jia, Yafang Shi, Xiaofeng Nie, Song Zhao, Tiecheng Wang, Virender K. Sharma %T Persistent free radicals in humin under redox conditions and their impact in transforming polycyclic aromatic hydrocarbons %0 Journal Article %D 2020 %J Front. Environ. Sci. Eng. %J Frontiers of Environmental Science & Engineering %@ 2095-2201 %R 10.1007/s11783-020-1252-y %P 73- %V 14 %N 4 %U {https://journal.hep.com.cn/fese/EN/10.1007/s11783-020-1252-y %8 2020-08-15 %X

• Regulation of redox conditions promotes the generation of free radicals on HM.

• HM-PFRs can be fractionated into active and inactive types depending on stability.

• The newly produced PFRs readily release electrons to oxygen and generate ROS.

• PFR-induced ROS mediate the transformation of organic contaminants adsorbed on HM.

The role of humic substance-associated persistent free radicals (PFRs) in the fate of organic contaminants under various redox conditions remains unknown. This study examined the characterization of original metal-free peat humin (HM), and HM treated with varying concentrations of H2O2 and L-ascorbic acid (VC) (assigned as H2O2-HM and VC-HM). The concentration of PFRs in HM increased with the addition of VC/H2O2 at concentrations less than 0.08 M. The evolution of PFRs in HM under different environmental conditions (e.g., oxic/anoxic and humidity) was investigated. Two types of PFRs were detected in HM: a relatively stable radical existed in the original sample, and the other type, which was generated by redox treatments, was relatively unstable. The spin densities of VC/H2O2-HM readily returned to the original value under relatively high humidity and oxic conditions. During this process, the HM-associated “unstable” free radicals released an electron to O2, inducing the formation of reactive oxygen species (ROS, i.e., OH and O2). The generated ROS promoted the degradation of polycyclic aromatic hydrocarbons based on the radical quenching measurements. The transformation rates followed the order naphthalene>phenanthrene>anthracene>benzo[a]pyrene. Our results provide valuable insight into the HM-induced transformation of organic contaminants under natural conditions.