Wavelength trends of photoproduction of reactive transient species by chromophoric dissolved organic matter (CDOM), under steady-state polychromatic irradiation

Abstract

The formation quantum yields of photochemically produced reactive intermediates (PPRIs) by irradiated CDOM (in this study, Suwannee River Natural Organic Matter and Upper Mississippi River Natural Organic Matter) decrease with increasing irradiation wavelength. In particular, the formation quantum yields of the excited triplet states of CDOM (³CDOM*) and of singlet oxygen (¹O₂) have an exponentially decreasing trend with wavelength. The ^•OH wavelength trend is different, because more effective ^•OH production occurs under UVB irradiation than foreseen by a purely exponential function. We show that the parameter-adjustable Weibull function (which adapts to both exponential and some non-exponential trends) is suitable to fit the mentioned quantum yield data, and it is very useful when CDOM irradiation is carried out under polychromatic lamps as done here. Model calculations suggest that, thanks to the ability of CDOM to also absorb visible radiation, and despite its decreasing quantum yield of ^•OH generation with increasing wavelength, CDOM would be able to trigger ^•OH photogeneration in deep waters, to a higher extent than UVB-absorbing nitrate or UVB + UVA-absorbing nitrite.

Keywords: Chromophoric dissolved organic matter; Hydroxyl radical; Polychromatic irradiation; Singlet oxygen; Triplet states; Weibull function.