Seasonal and Water Column Trends of the Relative Role of Nitrate and Nitrite as *OH Sources in Surface Waters

Based on literature data of sunlight spectrum, photolysis quantum yields, and absorption spectra, the relative role of nitrite and nitrate as *OH sources in surface waters was assessed, and its dependence on the season and the depth of the water column studied. In the majority of surface water samples (river, lake and seawater) nitrite is expected to play a more important role as *OH source compared to nitrate, in spite of the usually lower [NO₂^-] values. Interestingly, under the hypothesis of a constant ratio of the concentrations of nitrate and nitrite (to be corrected later on for the actual concentration ratio in a given sample), the relative role of nitrite compared to nitrate would be minimum in summer, at noon, in the surface layer of natural waters. Any decrease in the sunlight intensity that can be experienced in the natural environment (different season than summer, water column absorption, time of the day other than the solar noon), with its associated influence on the sunlight spectrum, would increase the relative role of nitrite compared to nitrate.