Reactivity of Triplet Excited States of Dissolved Natural Organic Matter in Stormflow from Mixed-Use Watersheds

Dissolved organic matter (DOM) quantity and composition control the rate of formation (R-f,R-T) of triplet excited states of dissolved natural organic matter ((DOM)-D-3*) and the efficiency of (DOM)-D-3* formation (the apparent quantum yield, AQY(T)). Here, the reactivity of (DOM)-D-3* in stormflow samples collected from watersheds with variable land covers is examined. Stormflow DOM reflects variability in DOM quantity and composition as a function of land cover and may be important in controlling the fate of cotransported pollutants. Rf,T and AQY(T) were measured using 2,4,6-trimethylphenol in stormflow samples under simulated sunlight. The DOM source and composition was characterized using absorbance and fluorescence spectroscopies and high resolution mass spectrometry. Rf,T and the total rate of light absorption by the water samples (R-a) increased with the dissolved organic carbon (DOC) concentration. AQY(T) was independent of DOC concentration, but varied with DOM source: developed land cover (4-6%) approximate to open water > vegetated land cover (3%). AQY(T) was positively related to an index for microbial/algal DOM content and negatively related to DOM molecular weight, DOM aromaticity, and the content of polyphenols. This work demonstrates that TMP is an effective probe for the determination of R-f,R-T and AQY(T) in whole water samples after accounting for the inhibition of TMP photodegradation by DOM.