Photolytic Aging of Secondary Organic Aerosol: Evidence for a Substantial Photo-Recalcitrant Fraction

Photolytic aging has been proposed as a major mass loss mechanism for atmospheric secondary organic aerosol (SOA). However, estimated mass loss rates vary by orders of magnitude, and their impacts on modeled SOA loadings and properties are highly uncertain. In this study, photolysis rates and composition changes of a-pinene SOA are analyzed in situ over multiple days in an environmental chamber. After an initial exponential decay (tau similar to 22 h), the mass loss rate slows dramatically, with more than similar to 70-90% of the SOA particulate mass undergoing an essentially negligible photolytic degradation. Scaled to ambient conditions, SOA undergoes rapid photolysis over only its first day in the atmosphere; beyond this, the remaining SOA is photo-recalcitrant, and photolysis ceases to be a major sink compared to wet deposition time scales. Thus, extrapolation of the initial photolysis loss rate to the entire aerosol mass may significantly overestimate the role of photolysis in the removal of atmospheric SOA.