Photolytic Mass Loss of Humic Substances Measured with a Quartz Crystal Microbalance.

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Laboratory studies have shown that photolytic mass loss can be a significant sink for secondary organic aerosol (SOA). Here, we use a quartz crystal microbalance to measure mass loss of Suwannee River Humic Acid (SRHA) and Suwannee River Fulvic Acid (SRFA), surrogates for SOA, exposed to 254, 300, and 405 nm radiation over the course of 24 h. We find that the photolytic mass loss rates of these materials are comparable to those for laboratory-generated limonene and toluene SOA material from the study of Baboomian et al, ACS Earth Space Chem. 2020, 4, 1078. Scaling our results to ambient conditions, we estimate that humic substances in aerosols can lose as much as 8% by mass in the first day of exposure in the atmosphere, equivalent to 0.025% of J NO2 , the photolysis rate of nitrogen dioxide. By using zero air instead of nitrogen, we also find that the presence of oxygen accelerates the photolytic mass loss rate by a factor of 2 to 4 at all wavelengths suggesting a potential role for reactive oxygen species. UV photolysis of an aqueous SRFA solution demonstrated both photobleaching at UV wavelengths and photoenhancement at visible wavelengths. Ultrahigh-resolution mass spectrometric analysis showed that condensed-phase SRFA photolysis led to decreased intensity in the 100-300 m/z range while aqueous SRFA photolysis resulted in an increase in intensity in the same range. This work reaffirms that photolytic mass loss is a potentially significant sink for SOA, but only on the time scale of a day or two and demonstrates that SRHA and SRFA are suitable surrogates for atmospheric SOA with respect to photolytic mass loss.