Isotopic Insights into Organic Composition Differences between Supermicron and Submicron Sea Spray Aerosol

To elucidate the seawater biological and physicochemical factors driving differences in organic composition between supermicron and submicron sea spray aerosol (SSA_super and SSA_sub), carbon isotopic composition (δ¹³C) measurements were performed on size-segregated, nascent SSA collected during a phytoplankton bloom mesocosm experiment. The δ¹³C measurements indicate that SSA_super contains a mixture of particulate and dissolved organic material in the bulk seawater. After phytoplankton growth, a greater amount of freshly produced carbon was observed in SSA_super with the proportional contribution being modulated by bacterial activity, emphasizing the importance of the microbial loop in controlling the organic composition of SSA_super. Conversely, SSA_sub exhibited no apparent relationship with biological activity but tracked closely with surface tension measurements probing the topmost ∼0.2-1.5 μm of the sea surface microlayer. This probing depth is similar to a bubble's film thickness at the ocean surface, suggesting that SSA_sub organic composition may be influenced by the presence of surfactants at the air-sea interface that are transferred into SSA_sub by bubble bursting. Our findings illustrate the substantial impact of seawater dynamics on the pronounced organic compositional differences between SSA_super and SSA_sub and demonstrate that these two SSA populations should be considered separately when assessing their contribution to marine aerosols and climate.