PNNL

Abstract

Polycyclic aromatic hydrocarbons (PAHs) known for their harmful health effects undergo long-range transport (LRT) when adsorbed on and/or absorbed in atmospheric particles. The association between atmospheric particles, PAHs, and their LRT has been the subject of many studies, yet remains poorly understood. Current models assume PAHs instantaneously attain reversible gas-particle equilibrium. In this paradigm, during LRT, as gas-phase PAHs concentrations are depleted due to oxidation and dilution, particle-bound PAHs rapidly evaporate to re-establish equilibrium, leading to severe underpredictions of LRT potential of particle-bound PAHs. Here we present a new, experimentally based picture, in which the PAHs become trapped inside highly viscous quasi-solid secondary organic aerosol (SOA) particles during particle formation, and thus prevented from evaporation, and shielded from oxidation. In contrast, surface-adsorbed PAHs rapidly evaporate, leaving no trace behind. We find synergetic effects between PAHs and SOA, in that the presence of PAHs inside SOA particles drastically slows SOA evaporation to the point that it can be ignored, and the highly viscous SOA prevents PAHs evaporation assuring efficient LRT. The data show that the assumptions of instantaneous reversible gas-particle equilibrium for PAHs and for SOA are fundamentally flawed, providing explanation for the persistent discrepancy between observed and predicted particle-bound PAHs.