The divergent effects of nitrate and ammonium application on mercury methylation, demethylation, and reduction in flooded paddy slurries

Abstract

The production of methylmercury (MeHg) in flooded paddy fields determines its accumulation in rice grains; this, in turn, results in MeHg exposure risks for not only rice-eating humans but also wildlife. Nitrogen (N) fertilizers have been widely applied in rice cultivation fields to supply essential nutrients. However, the effects of N fertilizer addition on mercury (Hg) transformations are not unclear. This limits our understanding of MeHg formation in rice paddy ecosystems. In this study, we spiked three Hg tracers (²⁰⁰Hg^II, Me¹⁹⁸Hg, and ²⁰²Hg⁰) in paddy slurries fertilized with urea, ammonium, and nitrate. The influences of N fertilization on Hg methylation, demethylation, and reduction and the underlying mechanisms were elucidated. The results revealed that dissimilatory nitrate reduction was the dominant process in the incubated paddy slurries. Nitrate addition inhibited Hg^II reduction, Hg^II methylation, and MeHg demethylation. Competition between nitrates and other electron acceptors (e.g., Hg^II, sulfate, or carbon dioxide) under dark conditions was the mechanism underlying nitrate-regulated Hg transformation. Ammonium and urea additions promoted Hg^II reduction, and anaerobic ammonium oxidation coupled with Hg^II reduction (Hgammox) was likely the reason. This work highlighted that nitrate addition not only inhibited Hg^II methylation but also reduced the demethylation of MeHg and therefore may generate more accumulation of MeHg in the incubated paddy slurries. Findings from this study link the biogeochemical cycling of N and Hg and provide crucial knowledge for assessing Hg risks in intermittently flooded wetland ecosystems.

Keywords: Flooded paddy soil; Mercury transformation; Multicompound specific isotope labeling; Nitrogen fertilization.