Mapping gaseous dimethylamine, trimethylamine, ammonia, and their particulate counterparts in marine atmospheres of China’s marginal seas – Part 2: Spatiotemporal heterogeneity, causes, and hypothesis

Spatiotemporal heterogeneities in the concentrations of alkaline gases and their particulate counterparts in the marine atmosphere over China's marginal seas were investigated in terms of causes and chemical conversion during two winter cruise campaigns, using semi-continuous measurements made by an onboard URG-9000D Ambient Ion Monitor-Ion Chromatograph (AIM-IC, Thermo Fisher). During the cruise campaign over the East China Sea from 27 December 2019 to 6 January 2020, the concentrations of gas-phase atmospheric trimethylamine (TMAgas) varied by approximately 1 order of magnitude, with an average (± standard deviation) of 0.10±0.04 µg m−3 corresponding to a mixing ratio of 26±17 pptv. Corresponding mean values were 0.037±0.011 µg m−3 (14±5 pptv in mixing ratio) over the Yellow Sea during the period from 7 to 16 January 2020 and 0.031±0.009 µg m−3 (12±4 pptv in mixing ratio) over the Yellow Sea and Bohai Sea from 9 to 22 December 2019. By contrast, the simultaneously observed concentrations of TMA in PM2.5, detected as TMAH+, over the East China Sea were 0.098±0.069 µg m−3 and substantially smaller than the 0.28±0.18 µg m−3 observed over the Yellow Sea and Bohai Sea from 9 to 22 December 2019. A significant correlation between TMAgas and particulate TMAH+ was observed over the East China Sea, but no correlation was found over the Yellow Sea and Bohai Sea. Proportional or disproportional variations in concentrations of TMAgas with particulate TMAH+ over the sea zones were probably attributed to the difference in the enrichment of TMAH+ in the sea surface microlayer. In addition, spatiotemporal heterogeneities in concentrations of atmospheric ammonia (NH3gas), atmospheric dimethylamine (DMAgas), and DMA in PM2.5, detected as DMAH+, were investigated. Case analyses were performed to illustrate the formation and chemical conversion of particulate aminium ions in marine aerosols. Finally, we hypothesized the release of basic gases and particulate counterparts from the ocean to the atmosphere, together with the secondary formation of DMAH+ and chemical conversion of TMAH+, in the marine atmosphere.