Probing the DOM-mediated photodegradation of methylmercury by using organic ligands with different molecular structures as the DOM model.

Photodegradation is the main depletion pathway for methylmercury (MeHg) in surface water. The formation of MeHg-dissolved organic matter (DOM) complexes has been found to be a key step in MeHg photodegradation. However, the major functional groups involved in the DOM-mediated process have yet to be clearly resolved. In this work, we systematically investigated the effects of DOM molecular structures on MeHg photodegradation by using a variety of organic ligands with different functional groups (e.g., thiosalicylate, thiophenol, and thioaniline). The results showed that thiol and phenyl groups may be the major functional groups governing DOM-mediated MeHg photodegradation, with photodegradation rates also dependent on the type (carboxyl, hydroxyl, and amino group) and position (ortho-, meta-, and para-) of other chemical substituents. The addition of "non-photochemically active" thiol ligands (e.g., mercaptoethanol and dithiothreitol) and high concentrations of Cl- can significantly inhibit the o-thiosalicylate-induced MeHg photodegradation, indicating that complexation of MeHg with these ligands is necessary for MeHg photodegradation. Sparging with O2 had a negligible effect on MeHg photodegradation, while sparging with N2 significantly enhanced MeHg photodegradation. This finding suggests that MeHg photodegradation may be a reductive process, which was further supported by identification of the degradation products of MeHg. A possible protonolysis mechanism of MeHg photodegradation in the presence of o-thiosalicylate was then proposed based on the findings of this study.