Sources and Transformation of Methylmercury in Paddy Water: Insights from Mercury Isotopes Collected by Diffusive Gradients in Thin Films

Despite concerns about methylmercury (MeHg) contamination in rice, the sources and transformation mechanisms of MeHg within paddy field water, the primary source of MeHg in rice, remain unclear. Determination of the isotopic composition of MeHg in paddy water is crucial to clarify these processes. However, there is a lack of sampling and analytical methods for quantifying MeHg isotopes in water samples. In this study, we use diffusive gradients in thin films (DGT) <i>in situ</i> to collect MeHg from paddy water to determine the concentration of MeHg and the associated isotopic composition. This technique enables high collection efficiency of aqueous MeHg with limited Hg isotope mass-dependent fractionation (∼- 0.2‰ δ²⁰²Hg) and mass-independent fractionation (<0.1‰ Δ¹⁹⁹Hg). Field applications using the developed DGT method suggest that <i>in situ</i> methylation of soluble Hg(II) drives the generation of MeHg in paddy water. MeHg in overlying water exhibits a Δ¹⁹⁹Hg/Δ²⁰¹Hg ratio of 1.07 ± 0.09, indicating significant photoreduction of aqueous Hg(II) before methylation. The absence of photodemethylation Δ¹⁹⁹Hg/Δ²⁰¹Hg ratio (∼1.36) suggests limited MeHg demethylation in the overlying water. This study provides insights into the sources and transformation of MeHg in rice paddies and helps develop mitigation strategies to reduce MeHg exposure through rice consumption.