Impact of OH Heterogenous Oxidation on the Evolution of Brown Carbon Aerosol Optical Properties

The effects of varying relative humidity (RH) on the evolution of brown carbon (BrC) optical properties induced by heterogeneous OH oxidation were investigated in a series of photooxidation chamber experiments. A BrC surrogate was generated from aqueous 1,3-dihydroxybenzene (10 mM) and H2O2 (10 mM) exposed to >300 nm radiation, atomized, passed through a series of trace gas denuders, and injected into the chamber, which was conditioned to about 10 or 60% RH. Following aerosol injection, H2O2 was continuously bubbled into the chamber; an hour later, the chamber was irradiated with black-lights (UV-B) to produce OH. Before irradiation, aerosol absorption and scattering at 405 nm, measured using a photoacoustic spectrometer, decreased due only to deposition and dilution, and single scattering albedo (SSA) was relatively steady. In the presence of gas-phase OH, absorption first increased, despite continued particle losses, and SSA decreased. Subsequently, absorption decreased faster than scattering, and SSA increased uniformly. At 60% RH, colour enhancement, likely associated with functionalization, was greatest after only minutes of reaction. In contrast, at 10% RH, peak colour enhancement occurred after about two hours of reaction, indicating that the decrease in RH and the attendant increase in particle viscosity significantly impeded heterogeneous OH oxidation of the BrC surrogate.