Dissolved organic matter (DOM) quantity and composition control the rate of formation (Rf,T) of triplet excited states of dissolved natural organic matter (3DOM∗) and the efficiency of 3DOM∗ formation (the apparent quantum yield, AQYT). Here, the reactivity of 3DOM∗ 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 AQYT 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 (Ra) increased with the dissolved organic carbon (DOC) concentration. AQYT was independent of DOC concentration, but varied with DOM source: developed land cover (4-6%) ≈ open water > vegetated land cover (3%). AQYT 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 Rf,T and AQYT in whole water samples after accounting for the inhibition of TMP photodegradation by DOM.
Bibliographical noteFunding Information:
We thank the many people who helped us collect the stormflow, baseflow, and snowmelt samples. Particularly we thank Eric Anderson, Yvette Christiansan, Matthew Kocian, Eric Korte, Jaimie Rockney, and Britta Suppes. We thank four undergraduate researchers, Dean Bock, Jeanne Moua, Conner Dunteman, and Josh Kirk. They were instrumental in sample processing and water chemistry measurements. We thank Amy McKenna and Yuri Corilo at the National High Magnetic Field Laboratory (NHMFL) for help with the FT-ICR MS analysis. NHMFL is supported by NSF DMR-117490, the Future Fuels Institute, and the State of Florida. We gratefully acknowledge funding from the Minnesota Environmental and Natural Resources Trust fund as recommended by the Legislative and Citizen Commission on Minnesota Resources, a Doctoral Dissertation Fellowship from the Graduate School at the University of Minnesota, and the National Science Foundation (CBET-143414).
© 2017 American Chemical Society.