LAUSR

Recently, there has been increasing interest in reducing methylmercury (MeHg) phytoavailability using biochar, although the underlying mechanisms are not fully understood. By combining lab-scale batch incubation with pot and field validations, we demonstrate that biochar-impacted sulfur cycling in soils and MeHg-soil binding play key roles in controlling MeHg phytoavailability. (1) Under anoxic conditions, biochar-associated sulfate and biochar-facilitated microbial sulfate reduction enhanced the production of reduced inorganic sulfur species as acid-volatile sulfide (AVS) in soils by 122%, facilitating MeHg binding with soils and thus reducing MeHg phytoavailability. (2) In contrast, under oxic conditions, the reduced inorganic sulfur was oxidized (resulting in a 68-91% decrease in AVS), which released soil-bound MeHg and increased MeHg phytoavailability. The proposed mechanisms could explain the distinct effects of biochar amendment on MeHg bioaccumulation observed under anoxic (10-88% lower in rice grains) and oxic conditions (48-84% higher in wheat grains). Our results dispute the commonly held assumption that reduced MeHg phytoavailability under biochar amendment can be primarily attributed to MeHg-biochar binding. Therefore, the potential increased risk of MeHg in oxic soils following biochar amendment should be evaluated in more detail.