Photogeneration of reactive transient species upon irradiation of natural water samples: Formation quantum yields in different spectral intervals, and implications for the photochemistry of surface waters

• Quantum yields decrease with increasing wavelength.
• The decrease is less marked for 1O2 compared to 3CDOM* and OH.
• The photochemistry of HMW CDOM is likely involved in these effects.
• Significant but moderate variability of quantum yields in different environments.
• The findings have important implications for photochemical modelling.

Chromophoric dissolved organic matter (CDOM) in surface waters is a photochemical source of several transient species such as CDOM triplet states (3CDOM*), singlet oxygen (1O2) and the hydroxyl radical (OH). By irradiation of lake water samples, it is shown here that the quantum yields for the formation of these transients by CDOM vary depending on the irradiation wavelength range, in the order UVB > UVA > blue. A possible explanation is that radiation at longer wavelengths is preferentially absorbed by the larger CDOM fractions, which show lesser photoactivity compared to smaller CDOM moieties. The quantum yield variations in different spectral ranges were definitely more marked for 3CDOM* and OH compared to 1O2. The decrease of the quantum yields with increasing wavelength has important implications for the photochemistry of surface waters, because long-wavelength radiation penetrates deeper in water columns compared to short-wavelength radiation. The average steady-state concentrations of the transients (3CDOM*, 1O2 and OH) were modelled in water columns of different depths, based on the experimentally determined wavelength trends of the formation quantum yields. Important differences were found between such modelling results and those obtained in a wavelength-independent quantum yield scenario.

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