Possible Effect of Climate Change on Surface-Water Photochemistry: A Model Assessment of the Impact of Browning on the Photodegradation of Pollutants in Lakes during Summer Stratification. Epilimnion vs. Whole-Lake Phototransformation

Water browning in lakes (progressive increase of the content of chromophoric dissolved organic matter, CDOM) has the potential to deeply alter the photodegradation kinetics of pollutants during summer stratification. Browning, which takes place as a consequence of climate change in several Nordic environments, causes the thermocline to be shallower, because higher CDOM decreases the penetration of sunlight inside the water column. Using a model approach, it is shown in this paper that pollutants occurring in the epilimnion would be affected differently depending on their main photodegradation pathway(s): almost no change for the direct photolysis, slight decrease in the degradation kinetics by the hydroxyl radicals ((OH)-O-center dot, but the resulting degradation would be too slow for the process to be effective during summer stratification), considerable decrease for the carbonate radicals (CO3 center dot-), increase for the excited triplet states of CDOM ((CDOM)-C-3*) and singlet oxygen (O-1(2)). Because it is difficult to find compounds that are highly reactive with CO(3)(center dot-)and poorly reactive with(3)CDOM*, the degradation rate constant of many phenols and anilines would show a minimum with increasing dissolved organic carbon (DOC), because of the combination of decreasing CO(3)(center dot-)and increasing(3)CDOM* photodegradation. In contrast, overall photodegradation would always be inhibited by browning when the whole water column (epilimnion + hypolimnion) is considered, either because of slower degradation kinetics in the whole water volume, or even at unchanged overall kinetics, because of unbalanced distribution of photoreactivity within the water column.