Mechanism of Cr(VI) reduction by humin: Role of environmentally persistent free radicals and reactive oxygen species

Abstract

Humic substances, especially humin (HM) in its solid phase, is considered to be the main electron donor during the reduction of Cr(VI) in the environment. This work explores the reaction mechanism between Cr(VI) and the functional groups contained in HM, environmentally persistent free radicals (EPFRs), and reactive oxygen species (ROS). We examine the changes in the functional groups, EPFRs, and ROS on HM during the reaction, and inhibit the production of ROS to verify their effect. Our results demonstrate that the carboxyl and phenolic hydroxyl groups contained in HM are consumed during the reaction. The phenolic hydroxyl group can directly react with Cr(VI) as an electron donor, and can also transfer electrons to molecular oxygen to generate superoxide radicals to reduce Cr(VI). EPFRs also exhibit the same reaction pathway. The molecular oxygen in the solution gains electrons to generate O2·-, which further reacts with Cr(VI) to reduce it to Cr(III). The production and effect of active oxygen are verified by removing oxygen from the solution. In this study, the contribution of active oxygen to the reduction of Cr(VI) is approximately 30%. This study provides theoretical support for revealing the effects of humic substances on the conversion of Cr(VI).