Surface Crust Formation Controls Evaporation Kinetics of Secondary Organic Aerosols

Gas-particle partitioning is critical for the evolution of secondary organic aerosols (SOA) in the atmosphere. SOA particles evaporate more slowly than expected at nearly size-independent rates, but the underlying mechanism remains controversial. Here, we apply kinetic multilayer modeling to simulate evaporation of α-pinene SOA, demonstrating that surface crust formation, emerging from accumulation of low-volatility compounds at the particle surface, leads to slow evaporation and reduced size dependence of the evaporation rate. While evaporation induced by decomposition of oligomers would naturally lead to size-independent evaporation rates, we observe and simulate nearly size-independent slow evaporation of polyethylene glycol mixture particles containing polymeric species that do not decompose, confirming the relevance of composition-dependent diffusivity for size-independent, slow evaporation. Slow evaporation of limonene SOA was also observed in environmental chamber experiments, and model simulations demonstrate strong surface crust formation with bulk diffusivity being depressed by up to 5 orders of magnitude compared to the inner bulk. We present experimental evidence using a surface-based mass spectrometry technique that shows that the particle surface becomes enriched in high molecular weight compounds upon evaporation of monomers. Our findings imply that viscous surface crusts may also limit the growth and chemical transformation of SOA particles, influencing their impacts on air quality and climate.