Photochemical demethylation of methylmercury (MeHg) in aquatic systems: A review of MeHg species, mechanisms, and influencing factors

Photodemethylation is the major pathway of methylmercury (MeHg) demethylation in surface water before uptake by the food chain, whose mechanisms and influence factors are still not completely understood. Here, we review the current knowledge on photodemethylation of MeHg and divide MeHg photolysis into three pathways: (1) direct photodemethylation, (2) free radical attack, and (3) intramolecular electron or energy transfer. In aquatic environments, dissolved organic matter is involved into all above pathways, and due to its complex compositions, properties and concentrations, DOM poses multiple functions during the PD of MeHg. DOM-MeHg complex (mainly by sulfur-containing molecules) might weaken the C-Hg bond and enhance PD through both direct and indirect pathways. In special, synergistic effects of both strong binding sites and chromophoric moieties in DOM might lead to intramolecular electron or energy transfer. Moreover, DOM might play a role of radical scavenger; while triplet state DOM, which is generated by chromophoric DOM under light, might become a source of free radicals. Apart from DOMs, transition metals, halides, NO3-, NO2-, and carbonates also act as radical initialaters or scavengers, and significantly pose effects on radical demethylation, which is generally mediated by hydroxyl radicals and singlet oxygen. Environmental factors such as pH, light wavelength, light intensity, dissolved oxygen, salinity, and suspended particles also affect the PD of MeHg. This study assessed previously published works on three major mechanisms, with the goal of providing general estimates for photodemethylation under various environment factors according to know effects, and highlighting the current uncertainties for future research directions.