Ocean Emission Pathway and Secondary Formation Mechanism of Aminiums Over the Chinese Marginal Sea

Abstract

AbstractAmines/aminiums are recognized for their importance in new particle formation, organic nitrogen cycle, and aerosol forcings. Among the complex sources, the ocean origins and generation pathways of aminiums are less understood. During a cruise campaign over the Chinese marginal sea (Bohai Sea), five low‐molecular‐weight aminiums were measured. The strong anthropogenic period (terrestrial transport) and the weak anthropogenic period (dust, clean, and sea fog periods) were identified based on the traceable aerosol chemical species, air masses transport patterns, and marine chlorophyll‐a. Inconsistent spatiotemporal variations of various aminiums were observed. Monomethylaminium (MMAH+), dimethylaminium (DMAH+), ethylaminium (EAH+), and diethylaminium (DEAH+) were more enriched during the weak anthropogenic period than the strong anthropogenic period and especially peaked during the sea fog period. The significant correlation between the four aminiums and methanesulfonic acid suggested their secondary formation pathways. Through further exploring the governing factors, the acid–base neutralization via the aqueous phase processing was identified as a critical process for the secondary transformation of aminiums. In contrast, trimethylaminium (TMAH+) showed moderate correlation with Na+ in the total suspended particles only, suggesting its primary marine sources via enrichment in the sea‐spray aerosol through bubble bursting. Based on the step‐wise correlation analysis, the sea surface organic nitrogenous reservoir was found as the dominant contributor to the measured aminiums over the Bohai Sea, while the role of marine phytoplankton emission in the formation of aminiums was limited.