Influence of the surface microlayer on atmospheric deposition of aerosols and polycyclic aromatic hydrocarbons

Atmospheric dry deposition is an important process for the introduction of aerosols and pollutants to aquatic environments. The objective of this paper is to assess, for the first time, the influence that the aquatic surface microlayer plays as a modifying factor of the magnitude of dry aerosol deposition fluxes. The occurrence of a low surface tension (ST) or a hydrophobic surface microlayer has been generated by spiking milli-Q water or pre-filtered seawater with a surfactant or octanol, respectively. The results show that fine mode (< 2.7 mu m) aerosol phase PAHs deposit with fluxes 2-3 fold higher when there is a low ST aquatic surface due to enhanced sequestration of colliding particles at the surface. Conversely, for PAHs bound to coarse mode aerosols (> 2.7 mu m), even though there is an enhanced deposition due to the surface microlayer for some sampling periods, the effect is not observed consistently. This is due to the importance of gravitational settling for large aerosols, rendering a lower influence of the aquatic surface on dry deposition fluxes. ST (mNm(-1)) is identified as one of the key factor driving the magnitude of PAH dry deposition fluxes (ng m(-2) d(-1)) by its influence on PAH concentrations in deposited aerosols and deposition velocities (upsilon(d), cms(-1)). Indeed, upsilon(d) values are a function of ST as 2 obtained by least square fitting and given by Ln(upsilon(d)) = -1.77 Ln(ST) + 5.74 (r(2) = 0.95) under low wind speed (average 4ms(-1)) conditions. (c) 2007 Elsevier Ltd. All rights reserved.