Singlet oxygen in the coupled photochemical and biochemical oxidation of dissolved organic matter

Dissolved organic matter (DOM) is a significant (>700 Pg) global C pool. Transport of terrestrial DOM to the inland waters and coastal zones represents the largest flux of reduced C from land to water (215 Tg yr^-1) (Meybeck, M. Am. J. Sci. 1983, 282, 401-450). Oxidation of DOM by interdependent photochemical and biochemical processes largely controls the fate of DOM entering surface waters. Reactive oxygen species (ROS) have been hypothesized to play a significant role in the photooxidation of DOM, because they may oxidize the fraction of DOM that is inaccessible to direct photochemical degradation by sunlight. We followed the effects of photochemically produced singlet oxygen (¹O₂) on DOM by mass spectrometry with ¹⁸O-labeled oxygen, to understand how ¹O ₂-mediated transformations of DOM may lead to altered DOM bioavailability. The photochemical oxygen uptake by DOM attributed to ¹O₂ increased with DOM concentration, yet it remained a minority contributor to photochemical oxygen uptake even at very high DOM concentrations. When DOM samples were exposed to ¹O ₂-generating conditions (Rose Bengal and visible light), increases were observed in DOM constituents with higher oxygen content and release of H₂O₂ was detected. Differential effects of H ₂O₂ and ¹O₂-treated DOM showed that ¹O₂-treated DOM led to slower bacterial growth rates relative to unmodified DOM. Results of this study suggested that the net effect of the reactions between singlet oxygen and DOM may be production of partially oxidized substrates with correspondingly lower potential biological energy yield.