Tracing human footprint and the fate of atmospheric polycyclic aromatic hydrocarbons over the Pearl River Estuary, China: Importance of particle size

Highlights: • Airborne PAHs were mostly derived from vehicle emission and combustion sources. • Gas−particle partitioning of size-segregated PAHs varied with particle diameters. • Dry deposition flux of ∑₂₃PAHs was dominated by those in coarse particles. • Seawater of the PRE was likely to contribute lower MW PAHs to the atmosphere. Few studies have focus on size-segregated particulate polycyclic aromatic hydrocarbons (PAHs) in the oceanic atmosphere. To better understand the impacts of anthropogenic activities on atmospheric PAHs, a heavily human-impacted estuary, the Pearl River Estuary (PRE), was chosen as a case study. We collected gaseous and size-segregated particulate samples of ambient air at two sites in the PRE, as well as from the exhaust emissions of the cruise ship used in the sampling campaign. In addition, surface seawater samples were collected. Size distribution patterns of high molecular-weight (HMW) particulate PAHs were bimodal at one site and unimodal at the other, suggesting PAHs at the former site were derived not only from long-range atmospheric transport but also from local sources. Gas–particle partition coefficients of HMW PAHs in size-segregated particles varied with particle sizes, mostly higher in fine particles (23PAHs (defined as the sum of 23 PAHs) was contributed mainly from coarse particles (>1.8 μm), and HMW PAHs with lower dry deposition velocities could be transported farther away. With respect to air–water exchange, lower MW PAHs tended to have net volatilization, whereas higher MW PAHs were likely to have net deposition. This study sheds new lights on the origins and fate of atmospheric PAHs over the PRE, and suggests the emissions of maritime traffics should be regulated. Collected near the metropolitan regions, atmospheric PAHs over the PRE were highly affected by anthropogenic activities, especially for HMW PAHs, which could pose a long-lasting impact to the oceanic atmosphere and marine organisms.