Secondary formation dominated low molecular weight amines origins in aerosols over the marginal seas of China

Abstract

Atmospheric low molecular weight amines play important roles in aerosol physiochemical properties and climate. However, the compositions, sources, and secondary formation mechanisms of amines in offshore aerosols remain unclear. Here, an integrated observation of methylamine (MA), ethylamine (EA), dimethylamine (DMA), iso-propanamine (IPA), propanamine (PA), “trimethylamine + diethylamine” (TMDEA), and over 100 other chemical components was conducted in total suspended particles samples collected during a spring 2018 research cruise across the Yellow Sea and Bohai Sea, China. Concentrations of total amines exhibited a north-to-south gradient from the Bohai Sea to the South Yellow Sea, corresponding to the decreasing influence of terrestrial air masses. Source analyses of amines were performed using specific organic molecular tracers representing primary biogenic sources, higher plant waxes, marine/microbial sources, biogenic secondary organic aerosols, biomass burning, and fossil fuel combustion, and two major secondary formation pathways were inferred. MA, EA, and DMA were largely influenced by terrestrial biogenic and anthropogenic sources, with the majority (74.0 %, 52.6 %, and 65.7 %) formed via nitrate-associated secondary formation pathways. PA was mainly derived from combustion-related sources along with terrestrial and marine biogenic contributions. In contrast, the predominant TMDEA was mostly generated via sulfate-associated secondary formation pathways (61.8 %) and contributed by marine emissions, resulting in spatial pattern distinct from other major amines and the north-to-south increasing relative contributions of amines in aerosols. These results highlight the impact of terrestrial emissions on offshore aerosol chemistry and the importance of origins and multiphase chemistry of amines under varying ambient conditions.