Photobleaching of chromophoric dissolved organic matter (CDOM) in rainwater

Significant photodegradation of chromophoric dissolved organic matter (CDOM) in rainwater was observed after exposure to simulated sunlight. Fluorescence excitation emission spectra (EEMS) of precipitation revealed the presence of four major peaks all of which degraded upon photolysis with the greatest loss in the region characteristic of marine CDOM. Photobleaching of absorbance also occurred in the wavelength region between 250 and 375 nm with the greatest loss of absorbance in the upper end of the UV-A region near 275 nm. There was a strong positive correlation between absorbance loss and total integrated fluorescence loss suggesting these optical properties and the degree to which they are photobleached in rainwater are directly related. The quantum yield of CDOM photodegradation in rainwater decreased dramatically with increasing wavelength and decreasing energy of incoming radiation with the average quantum yield at 325 nm approximately an order of magnitude greater than at 460 nm. The similarity of photolytic response between rainwater and Cape Fear estuarine CDOM indicates that some fraction of the compounds that make up rainwater CDOM may be derived from surface sources and/or that the processes that produce or modify humic-like substances in the atmosphere result in similar types of compounds as non-atmospheric processes.