Diel variations in photoinduced oxidation of Hg0 in freshwater

Experiments have been conducted to determine diel variations in photoinduced Hg0 oxidation in lake water under natural Hg(aq)0 concentrations. Pseudo-first-order rates of photooxidation (k′) were calculated for water freshly collected in a Canadian Shield lake, Lake Croche (45°56′ N, 74°00′ W), at different periods of the day and subsequently incubated in the dark. Hg0 oxidation rates ranged from 0.02 to 0.07 h−1, increasing from sunrise to noon and then decreasing throughout the remainder of the day. These changes paralleled those in sunlight intensity integrated over 1 h preceding water collection, and suggested that the water freshly collected in daylight was rich in photochemically produced Hg0 oxidants. It was also estimated that under intense solar radiation, even if oxidation rates reached a peak, reduction of Hg(II) was the prevalent redox process. Inversely, Hg0 oxidation overcame DGM production during the night or at periods of weaker light intensity. Overall, these findings explain the decreases in the DGM pool generally observed overnight. They also support previous reports that, during summer days, volatilization of Hg0 from water represent an important step in the Hg cycle in freshwater systems.