Effect of pH on photo-oxidation of dissolved organic carbon by hydroxyl radicals in a coloured, softwater stream

Abstract.

Previous work has shown that the photo-oxidation rate of dissolved organic carbon (DOC) exposed to solar radiation was significantly enhanced in acidic stream waters and that the average photo-oxidative loss of DOC in the UVA region was more than 60%. This study examined the effect of pH on photobleaching and the photo-oxidative loss of DOC and the degree of photo-oxidative loss by hydroxyl radicals (•OH) over the pH range 4–9 in a coloured, softwater stream. Binding iron with NaF lowered the photo-oxidation rate constant by about 50% at pH 4 and by 10–20% at pH 4.6 and 4.9. Hence, iron plays an important role in the photo-oxidative loss of DOC at pH 4 with declining importance as the pH increases. The importance of •OH in photo-oxidative loss of stream DOC was evaluated by adding KI to quench •OH. After 69 hours of artificial irradiation without KI, DOC loss decreased as pH increased from pH 4 to 9 whereas the minimum loss of absorbance at 300 nm occurred at pH 7. KI significantly reduced loss of DOC at pH 4, 5 and 7 but not at pH 9 with the fraction of DOC lost by non-•OH mechanisms gradually increasing from 58% to 75% between pH 4 and 7, and 100% at pH 9. Since many northern freshwater lakes on the Precambrian Shield receive large fluxes of UV-labile humic matter from peatlands and have pH < 7.5, photo-oxidative loss of DOC by both non-•OH and •OH mechanisms is important in C dynamics in northern freshwaters but with photo-oxidative loss dominated by non-•OH mechanisms likely operating in the UVA region.