Synergistic Photogeneration of Reactive Oxygen Species by Dissolved Organic Matter and C60 in Aqueous Phase

We investigated the photogeneration of reactive oxygen species (ROS) by C60 under UV irradiation, when humic acid (HA) or fulvic acid (FA) is present. When C60 and dissolved organic matter (DOM) were present as a mixture, singlet oxygen (1O2) generation concentrations were 1.2–1.5 times higher than the sum of 1O2 concentrations that were produced when C60 and DOM were present in water by themselves. When C60 and HA were present as a mixture, superoxide radicals (O2•–) were 2.2–2.6 times more than when C60 and HA were present in water by themselves. A synergistic ROS photogeneration mechanism involved in energy and electron transfer between DOM and C60 was proposed. Enhanced 1O2 generation in the mixtures was partly due to 3DOM* energy transfer to O2. However, it was mostly due to 3DOM* energy transfer to C60 producing 3C60*. 3C60* has a prolonged lifetime (>4 μs) in the mixture and provides sufficient time for energy transfer to O2, which produces 1O2. The enhanced O2•– generation for HA/C60 mixture was because 3C60* mediated electron transfer from photoionized HA to O2. This study demonstrates the importance of considering DOM when investigating ROS production by C60.