On the impacts of phytoplankton-derived organic matter on the properties of the primary marine aerosol – Part 1: Source fluxes

Abstract. The effect of biogenic dissolved and colloidal organic matter on the production of submicron primary sea-spray aerosol was investigated via the simulation of bubble bursting in seawater enriched with phytoplankton-released organics.

Seawater samples collected along a transect off the West African coast during the RHaMBLe cruise (RRS Discovery cruise D319), conducted as part of the SOLAS UK program, were analysed in order to identify the dominant oceanic algal species in a region of high biological activity. Cultures of microalgal strains representative of the species found in the collected seawater were grown in order to produce natural bioexudate. Colloidal plus dissolved organic fraction in this material remaining after <0.2 μm filtration was employed to prepare organic-enriched seawater proxies for the laboratory production of marine aerosol using a plunging-waterjet system as an aerosol generator. Submicron size distributions of aerosols generated from different organic monolayers and seawater proxies enriched with biogenic exudate were measured and compared with blanks performed with artificial seawater devoid of marine organics. A shift of the aerosol submicron size distribution toward smaller sizes and an increase in the production of particles with dry diameter (D_p0)<100 nm was repeatedly observed with increasing amounts of diatomaceous bioexudate in the seawater proxies used for aerosol generation. The effect was found to be sensitive to the organic carbon concentration in seawater and the algal exudate type. Diatomaceous exudate with organic carbon concentration (OC_{<0.2 μm}) >175 μM was required to observe a significant impact on the size distribution, which implies that effects are expected to be substantial only in high biological activity areas abundant with diatom algal populations. The laboratory findings were in agreement with analogous bubble-bursting experiments conducted with unfiltered oceanic seawater collected during the RHaMBLe cruise, which revealed a higher production of particles with D_p0<100 nm at regions with high biological activity. These findings suggest that the increase in the atmospheric aerosol modal sizes from winter to summer, reported by long-term observations in North Atlantic waters, is not directly due to an impact of the higher primary organic matter production occurring during warm periods.

A novel sub-micrometric size-resolved source flux function, explicitly defined as a function of the diatomaceous exudate concentration, was derived from the size distribution measurements and the estimation of the fractional whitecap coverage. According to the defined parameterisation, a 300 μM OC_{<0.2 μm} concentration of diatomaceous exudate in seawater produces an overall increment in the total source particle flux of ~20% with respect to the organics-free seawater case. The effect increases with decreasing particle size for D_p0<100 nm, resulting in multiplicative factors between 1.02–2 with respect to the particle flux generated from seawater devoid of marine organics. The total source flux derived from the presented parameterisation was compared to recent definitions of sea-spray source fluxes based on laboratory and field observations in the literature.