Bioavailability and methylation of bulk mercury sulfide in paddy soils: New insights into mercury risks in rice paddies

Abstract Mercury sulfide (HgS) constitutes the largest Hg reservoir in the lithosphere but has long been considered to be not bioavailable and a minor participant in Hg biogeochemical cycling. Herein, we report that bulk α-HgS can be dissolved and methylated in paddy soils, especially with rice culture. Bulk α-HgS exposure did not affect rice growth compared to the control group but significantly increased methylmercury (MeHg) contents in the rhizospheric soils (e.g., 80.15% and 108.71% higher for bulk α-HgS treatment vs. control at the seedling and maturation stages, respectively). Moreover, bulk α-HgS exposure induced an apparent accumulation of MeHg (50% higher for bulk α-HgS treatment vs. control) and markedly elevated total Hg (THg) in rice grains. The presence of DOM and reduced sulfide in paddy soils was further evidenced to drive the mobilization and dissolution of bulk α-HgS, thereby resulting in THg and MeHg accumulation in rice grains. These findings highlight the bioavailability of HgS in rice paddies and suggest that bulk HgS should be considered when assessing Hg health risks and developing efficient remediation approaches in Hg-contaminated croplands.