[Reduction and Oxidation of Mercury by Dissolved Organic Matter Under Anaerobic Conditions]

In sediments, wetlands, and flooded paddy soils, natural organic matter (DOM), such as humic acid (HA) and fulvic acid (FA), exist in a reduced state and mediate the reduction of Hg(Ⅱ) and affect the transformation of mercury and geochemical cycles. This study simulated a dark anaerobic environment to study the reduction of Hg(Ⅱ) by reduced HA and FA. Compared to oxidized HA and FA, the reduction capacity of the reduced HA and FA for Hg(Ⅱ) were higher. The optimal concentrations of reduced HA and FA to reduce Hg(Ⅱ) to Hg(0) were 0.2 mg·L^-1 and 1.5 mg·L^-1, respectively. The reduction quantity of Hg(Ⅱ) was enhanced with the increased concentration of reduced HA and FA at a lower than optimal concentration, whereas the reduction quantity of Hg(Ⅱ) decreased with increasing concentration of reduced HA and FA at a higher than optimal concentration due to the occurrence of thiol-competitive complexation. Hg(Ⅱ) was not reduced at a reduced HA concentration of 5 mg·L^-1. The kinetics results of Hg(Ⅱ) reduction demonstrated that the reduction rates were IHSS-HA > FRC-HA > FRC-FA at a low molar ratio (dissolved organic carbon (DOC):Hg(Ⅱ)=400:1). The reduction of Hg(Ⅱ) by the reduced HA stopped or processed in the opposite direction at a high molar ratio (DOC:Hg(Ⅱ)=10000:1). The quantity of Hg(0) decreased with increasing HA concentration. Furthermore, as the concentrations of reduced HA and FA were increased to 5 mg·L^-1 and 10 mg·L^-1, respectively, no Hg(0) was detected in the samples. The experiment of the recovery confirmed that reduced HA and FA reacted with Hg(0). Additionally, reduced HA, FA, and Hg(0) induced oxidative complexation with sulfhydryl or disulfide bonds. Reduced DOM played a dual role in Hg redox reactions, affecting the availability of active Hg, which, in turn, affected the methylation of microbial Hg.