Hydroxyl Radical Production from Irradiated Arctic Dissolved Organic Matter

The hydroxyl radical (OH·) plays an important role in the environmental chemistry and biogeochemistry of surface waters. OH· acts as a strong oxidant within the irradiated water column, and affects the bioavailability, cycling, and mineralization of dissolved organic matter (DOM), the speciation and redox state of important trace metals e.g., iron and copper, and the fate of persistent organic pollutants (POPs). The generation of this species from irradiated DOM may be especially important in Arctic surface waters during the boreal summer, which contains high levels of DOM and experiences continual solar irradiance. Here, we investigate the OH· produced from laser irradiated Arctic DOM isolated from Toolik Lake, AK (68°38′ N, 149°43′ W). We measured the wavelength dependence of OH· production for aqueous solutions of DOM and report that the greatest OH· production occurs at wavelengths less than 360 nm. OH· production rates ranged from 1.7 (±0.1)×10⁻⁷ M h⁻¹ to 6.4 (±0.2)×10⁻⁷ M h⁻¹, with the rate depending on both irradiation wavelength and to a lesser degree the method used to isolate the DOM matrix. These findings lead to a better understanding of the potentially important photo-oxidation processes that may impact DOM cycling in the Arctic.