Articles | Volume 15, issue 14
Atmos. Chem. Phys., 15, 7831–7840, 2015
Atmos. Chem. Phys., 15, 7831–7840, 2015

Research article 16 Jul 2015

Research article | 16 Jul 2015

Formation of hydroxyl radicals from photolysis of secondary organic aerosol material

K. M. Badali, S. Zhou, D. Aljawhary, M. Antiñolo, W. J. Chen, A. Lok, E. Mungall, J. P. S. Wong, R. Zhao, and J. P. D. Abbatt K. M. Badali et al.
  • University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6, Canada

Abstract. This paper demonstrates that OH radicals are formed by photolysis of secondary organic aerosol (SOA) material formed by terpene ozonolysis. The SOA is collected on filters, dissolved in water containing a radical trap (benzoic acid), and then exposed to ultraviolet light in a photochemical reactor. The OH formation rates, which are similar for both α-pinene and limonene SOA, are measured from the formation rate of p-hydroxybenzoic acid as measured using offline HPLC analysis. To evaluate whether the OH is formed by photolysis of H2O2 or organic hydroperoxides (ROOH), the peroxide content of the SOA was measured using the horseradish peroxidase-dichlorofluorescein (HRP-DCF) assay, which was calibrated using H2O2. The OH formation rates from SOA are 5 times faster than from the photolysis of H2O2 solutions whose concentrations correspond to the peroxide content of the SOA solutions, assuming that the HRP-DCF signal arises from H2O2 alone. The higher rates of OH formation from SOA are likely due to ROOH photolysis, but we cannot rule out a contribution from secondary processes as well. This result is substantiated by photolysis experiments conducted with t-butyl hydroperoxide and cumene hydroperoxide which produce over 3 times more OH than photolysis of equivalent concentrations of H2O2. Relative to the peroxide level in the SOA and assuming that the peroxides drive most of the ultraviolet absorption, the quantum yield for OH generation from α-pinene SOA is 0.8 ± 0.4. This is the first demonstration of an efficient photolytic source of OH in SOA, one that may affect both cloud water and aerosol chemistry.

Short summary
This is the first paper to demonstrate that SOA material forms OH radicals upon UV illumination. We quantify the OH formation rates in solution and show species other than H2O2, mostly probably ROOH molecules, are the likely source of the OH. The importance of an OH source from SOA is that photochemical processing within both cloudwater and aerosol particles may arise subsequent to the formation of these radicals.
Final-revised paper