Recent analyses of atmospheric aerosols from different regions have demonstrated the ubiquitous presence of strong surfactants and evidenced surface tension values, σ, below 40 mN m(-1), suspected to enhance the cloud-forming potential of these aerosols. In this work, this approach was further improved and combined with absolute concentration measurements of aerosol surfactants by colorimetric titration. This analysis was applied to PM2.5 aerosols collected at the Baltic station of Askö, Sweden, from July to October 2010. Strong surfactants were found in all the sampled aerosols, with σ = (32-40) ± 1 mN m(-1) and concentrations of at least 27 ± 6 mM or 104 ± 21 pmol m(-3). The absolute surface tension curves and critical micelle concentrations (CMC) determined for these aerosol surfactants show that (1) surfactants are concentrated enough in atmospheric particles to strongly depress the surface tension until activation, and (2) the surface tension does not follow the Szyszkowski equation during activation but is nearly constant and minimal, which provides new insights on cloud droplet activation. In addition, both the CMCs determined and the correlation (R(2) ∼ 0.7) between aerosol surfactant concentrations and chlorophyll-a seawater concentrations suggest a marine and biological origin for these compounds.
Surfactants
account for minor fractions of total organic carbon
in the ocean but can significantly influence the production of primary
marine aerosol particles (PMA) at the sea surface via modulation of
bubble surface tension. During September and October 2016, model PMA
(mPMA) were produced from seawater by bursting bubbles at two biologically
productive and two oligotrophic stations in the western North Atlantic
Ocean. Total concentrations of surfactants extracted from mPMA and
seawater were quantified and characterized via measurements of surface
tension isotherms and critical micelle concentrations (CMCs). Surfactant
CMCs in biologically productive seawater were lower than those in
the oligotrophic seawater suggesting that surfactant mixtures in the
two regions were chemically distinct. mPMA surfactants were enriched
in all regions relative to those in the associated seawater. Surface
tension isotherms indicate that mPMA surfactants were weaker than
corresponding seawater surfactants. mPMA from biologically productive
seawater contained higher concentrations of surfactants than those
produced from oligotrophic seawater, supporting the hypothesis that
seawater surfactant properties modulate mPMA surfactant concentrations.
Diel variability in concentrations of seawater and mPMA surfactants
in some regions is consistent with biological and/or photochemical
processing. This work demonstrates direct links between surfactants
in mPMA and those in the associated seawater.
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