Fog composition at Baengnyeong Island in the eastern Yellow Sea: detecting markers of aqueous atmospheric oxidations

Abstract

Abstract. Samples of fog water were collected at Baengnyeong Island (BYI) in the Yellow Sea during the summer of 2014. The most abundant chemical species in the fog water were NH4+ (mean of 2220 µM), NO3− (1260 µM), SO4−2 (730 µM), and Na+ (551 µM), with substantial contributions from other species consistent with marine and biomass burning influence on some dates. The pH of the samples ranged between 3.48 and 5.00, with a mean of 3.94, intermediate within pH values of fog/cloud water reported previously in Southeast Asia. Back trajectories (72 h) showed that high relative humidity ( >  80 %) was encountered upwind of the sampling site by all but one of the sampled air masses, and that the fog composition at BYI can be impacted by several different source regions, including the Sea of Japan, southeastern China, northeastern China, and the East China Sea. Sulfur in the collected fog was highly oxidized: low S(IV) concentrations were measured (mean of 2.36 µM) in contrast to SO4−2 and in contrast to fog/cloud S(IV) concentrations from pollutant source regions; organosulfate species were also observed and were most likely formed through aging of mainly biogenic volatile organic compounds. Low-molecular-mass organic acids were major contributors to total organic carbon (TOC; 36–69 %), comprising a fraction of TOC at the upper end of that seen in fogs and clouds in other polluted environments. Large contributions were observed from not only acetic and formic acids but also oxalic, succinic, maleic, and other organic acids that can be produced in aqueous atmospheric organic processing (AAOP) reactions. These samples of East Asian fog water containing highly oxidized components represent fog downwind of pollutant sources and can provide new insight into the fate of regional emissions. In particular, these samples demonstrate the result of extensive photochemical aging during multiday transport, including oxidation within wet aerosols and fogs.