Enrichment of short-chain organic acids transferred to submicron sea spray aerosols

Abstract

Organic acids, considered to be a substantial component of the marine carbon cycle, can enter the atmosphere through sea spray aerosol (SSA) and further affect the climate. Despite their importance, the distribution and mixing state of organic acids in SSA over the marine boundary layer are poorly understood and therefore need more investigation. Here, we have used ion chromatography (IC) in anion mode to measure short-chain organic acids concentrations in SSA collected throughout a custom-made SSA simulation chamber. The enrichment behavior and morphology of monocarboxylic acids (MAs, C1–8) and dicarboxylic acids (DAs) in submicron SSA were studied in seawater. We found that with MAs addition, the number concentration and mass concentration of SSA particles decreased gradually for C5–8 MAs, whereas they weakly varied with DAs addition due to the fact that carboxyl groups at both ends of DAs increased the surface tension of seawater. Moreover, the target compounds in submicron SSA displayed a surface activity-dependent enrichment behavior, where seawater with stronger surface activity, such as that containing MAs with >5 carbons, was more enriched in SSA in comparison to seawater with weaker surface activity. MAs with chain length <5 carbons were slightly enriched in SSA, whereas the enrichment factor (EF) of C5–8 MAs further increased with increasing chain length. These findings are of utmost importance in further understanding and quantifying the contribution of organic matter to SSA, which is crucial for assessing the atmosphere feedback of the marine carbon cycle. Main finding of the workSurface tension of seawater is the key factor affecting the enrichment of short-chain organic acids in SSA.