Impact of sulfur-impregnated biochar amendment on microbial communities and mercury methylation in contaminated sediment

S-impregnation of biochar through elemental S streaming is known to increase its sorption performance against Hg and methyl mercury (MeHg). However, the effects of %S-loading on biochar's mechanism and sorption capacities for MeHg, and its consequent impact when used as an amendment material for Hg-contaminated sediments, are poorly understood, and thus, were investigated in this work. Our results showed that a minimum sulfur loading of 1% was the most effective in reducing MeHg levels in sediments. At higher %S-loading (3-20%), the reduction in surface area, pore blockage due to unreacted sulfur particles, and presence of poorly bound sulfur species resulted in lowered effectiveness for MeHg control. Increasing S-functionalization during impregnation shifted the sorption process of MeHg from Hg-O to Hg-S in S-impregnated biochar (BCS). Our 60-day slurry experiment showed a significant reduction in pore water THg (40-70%) and MeHg (30-55%), as well as sediment MeHg (50-60%) in biochar-amended sediments. The reduction in the bioavailable Hg resulted in lowered Hg methylation, as supported by the suppression of both the Fe- and SO42--reduction activities in the amended sediments. The microbial community structure in BCS-amended sediments showed a shift towards sulfur-consuming, iron-reducing, thiosulfate-oxidizing, and sulfate-reducing bacterial populations. At the genus level, the overall relative abundance of principal Hg methylators was also lower in the BCS treatment than in the unamended sediments. This study highlights the application of BCS as a promising strategy for remediation of Hg-contaminated sediments.