Polycyclic aromatic hydrocarbons in urban atmosphere of Guangzhou, China: Size distribution characteristics and size-resolved gas-particle partitioning

Abstract

Size distributions of thirteen polycyclic aromatic hydrocarbons (PAHs), elemental carbon (EC), and organic carbon (OC) in the range of 0.01–18 μm were measured using a nano Micro-Orifice Uniform Deposit Impactor (nano-MOUDI) in an urban location in Guangzhou, China in July 2006. PAH size distributions were fit with five modes and the respective mass median aerodynamic diameters (MMAD) are: Aitken mode (MMAD: ∼0.05 μm), three accumulation modes AMI, AMII, AMIII (MMAD: 0.13–0.17 μm, 0.4–0.45 μm, and 0.9–1.2 μm, respectively), and coarse mode (MMAD: 4–6 μm). Seven-ring PAH was mainly in AMII and AMIII. Five- and six-ring PAHs were found to be abundant in all the three AM. Three- and four-ring PAHs had a significant presence in the coarse mode in addition to the three AM. Size-resolved gas-particle partition coefficients of PAHs (Kp) were estimated using measured EC and OC data. The Kp values of a given PAH could differ by a factor of up to ∼7 on particles in different size modes, with the highest Kp associated with the AMI particles and the lowest Kp associated with the coarse mode particles. Comparison of calculated overall Kp with measured Kp values in Guangzhou by Yang et al. (2010) shows that adsorption on EC appeared to be the dominant mechanism driving the gas-particle partitioning of three- and four-ring PAHs while absorption in OM played a dominant role for five- and six-ring PAHs. The calculated equilibrium timescales of repartitioning indicate that five- to seven-ring PAHs could not achieve equilibrium partitioning within their typical residence time in urban atmospheres, while three- and four-ring PAHs could readily reach new equilibrium states in particles of all sizes. A partitioning flux is therefore proposed to replace the equilibrium assumption in modeling PAH transport and fate.