Synergetic effect of pyrrhotite and zero-valent iron on Hg(Ⅱ) removal in constructed wetland: Mechanisms of electron transfer and microbial reaction

Effective removal of mercury (Hg) from wastewater is significant due to its high toxicity, especially methylmercury (MeHg). Reducing of Hg(II) to Hg(0) in constructed wetlands (CWs) using iron-based materials is an effective strategy for preventing the formation of MeHg. However, the surface passivation of zero-valent iron (ZVI) limits its application. Herein, synergetic ZVI and pyrrhotite were utilized to enhance Hg removal in CWs. Results indicated that the removal of total Hg, dissolved Hg, and particulate Hg in CWs with ZVI and pyrrhotite were improved by 21.68 ± 0.76 %, 13.02 ± 0.88 %, and 22.27 ± 0.76 % compared to that with single ZVI or pyrrhotite. Pyrrhotite increased the surface corrosion of ZVI, thereby facilitating the process of iron reduction. The redox of iron promoted the generation of EPS, which could provide electrons for Hg(II) reduction. The sulfur also participates in electron transfer by driving the methylation of Hg and provides sulfides to form FeS-Hg complexes and HgS precipitation. The abundance of key enzymes that involved in iron reduction and Hg transformation was enhanced with the addition of ZVI and pyrrhotite. The synergetic of pyrrhotite and ZVI enhances the removal of Hg in CW, offering a promising technology for high-efficiency treatment of Hg. [Display omitted] •Pyrrhotite in constructed wetlands mitigated the zero-valent iron (ZVI) passivation.•Synergetic of ZVI and pyrrhotite enhanced the removal of various forms of Hg.•ZVI and pyrrhotite promoted the production of EPS, and humic acid-Hg precipitate.•Interactions among ZVI, pyrrhotite, and key enzymes contributed to Hg metabolism.