Photolytic Degradation of Methylmercury Enhanced by Binding to Natural Organic Ligands

Monomethylmercury is a neurotoxin that poses significant risks to human health1 due to its bioaccumulation in food webs. Sunlight degradation to inorganic mercury is an important component of the mercury cycle that maintains methylmercury at low concentrations in natural waters. Rates of photodecomposition, however, can vary drastically between surface waters2-5 for reasons that are largely unknown. Here, we show that photodegradation occurs through singlet oxygen, a highly reactive form of dissolved oxygen generated by sunlight irradiation of dissolved natural organic matter. The kinetics of degradation, however, depended on water constituents that bind methylmercury cations. Relatively fast degradation rates (similar to observations in freshwater lakes) applied only to methylmercury species bound to organic sulfur-containing thiol ligands such as glutathione, mercaptoacetate, and humics. In contrast, methylmercury-chloride complexes, which are dominant in marine systems, were unreactive. Binding by thiols lowered the excitation energy of the carbon-mercury bond on the methylmercury molecule6-7 and subsequently increased reactivity towards bond breakage and decomposition. Our results explain methylmercury photodecomposition rates that are relatively rapid in freshwater lakes2-4 and slow in marine waters5.