Abstract
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, but the resulting degradation would be too slow for the process to be effective during summer stratification), considerable decrease for the carbonate radicals (CO3•−), increase for the excited triplet states of CDOM (3CDOM*) and singlet oxygen (1O2). Because it is difficult to find compounds that are highly reactive with CO3•− and poorly reactive with 3CDOM*, 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 CO3•− and increasing 3CDOM* 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.
Highlights
The photoinduced transformation processes are important pathways for the attenuation of biorecalcitrant contaminants that occur in surface waters [1,2]
Because it is difficult to find compounds that are highly reactive with CO3 − and poorly reactive with 3 chromophoric dissolved organic matter (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 CO3 −
Sunlight is absorbed by naturally occurring compounds such as the chromophoric dissolved organic matter (CDOM), nitrate, and nitrite [5]
Summary
The photoinduced transformation processes are important pathways for the attenuation of biorecalcitrant contaminants that occur in surface waters [1,2] These processes are usually divided into direct photolysis, where the pollutant absorbs sunlight and is transformed as a consequence, and indirect photochemistry [3,4]. In the latter case, sunlight is absorbed by naturally occurring compounds (photosensitizers) such as the chromophoric dissolved organic matter (CDOM), nitrate, and nitrite [5]. The result is an increase in surface-water (C)DOM levels (browning), which could affect photoreactions by enhancing processes triggered by 3 CDOM* and 1 O2 , over those induced by OH, CO3 − and the direct photolysis [11,13]. Implications are considered, as well, for the photodegradation of pollutants that are homogeneously distributed within the whole water column before the onset of stratification
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