Organic aerosol (OA) is an important fraction of submicron aerosols. However, it is challenging to predict and attribute the specific organic compounds and sources that lead to observed OA loadings, largely due to contributions from secondary production. This is especially true for megacities surrounded by numerous regional sources that create an OA background. Here, we utilize in situ gas and aerosol observations collected on board the NASA DC-8 during the NASA–NIER KORUS-AQ (Korea–United States Air Quality) campaign to investigate the sources and hydrocarbon precursors that led to the secondary OA (SOA) production observed over Seoul. First, we investigate the contribution of transported OA to total loadings observed over Seoul by using observations over the Yellow Sea coupled to FLEXPART Lagrangian simulations. During KORUS-AQ, the average OA loading advected into Seoul was ∼1–3 µg sm⁻³. Second, taking this background into account, the dilution-corrected SOA concentration observed over Seoul was ∼140 $\mathrm{\mu }\mathrm{g}{\mathrm{sm}}^{-\mathrm{3}}{\mathrm{ppmv}}^{-\mathrm{1}}$ at 0.5 equivalent photochemical days. This value is at the high end of what has been observed in other megacities around the world (20–70 $\mathrm{\mu }\mathrm{g}{\mathrm{sm}}^{-\mathrm{3}}{\mathrm{ppmv}}^{-\mathrm{1}}$ at 0.5 equivalent days). For the average OA concentration observed over Seoul (13 µg sm⁻³), it is clear that production of SOA from locally emitted precursors is the major source in the region. The importance of local SOA production was supported by the following observations. (1) FLEXPART source contribution calculations indicate any hydrocarbons with a lifetime of less than 1 day, which are shown to dominate the observed SOA production, mainly originate from South Korea. (2) SOA correlated strongly with other secondary photochemical species, including short-lived species (formaldehyde, peroxy acetyl nitrate, sum of acyl peroxy nitrates, dihydroxytoluene, and nitrate aerosol). (3) Results from an airborne oxidation flow reactor (OFR), flown for the first time, show a factor of 4.5 increase in potential SOA concentrations over Seoul versus over the Yellow Sea, a region where background air masses that are advected into Seoul can be measured. (4) Box model simulations reproduce SOA observed over Seoul within 11 % on average and suggest that short-lived hydrocarbons (i.e., xylenes, trimethylbenzenes, and semi-volatile and intermediate-volatility compounds) were the main SOA precursors over Seoul. Toluene alone contributes 9 % of the modeled SOA over Seoul. Finally, along with these results, we use the metric ΔOA/ΔCO₂ to examine the amount of OA produced per fuel consumed in a megacity, which shows less variability across the world than ΔOA∕ΔCO.

The Aerosol Mass Spectrometer (AMS) and Aerosol Chemical Speciation Monitor (ACSM) are widely used for quantifying submicron aerosol mass concentration and composition, in particular for organic aerosols (OA). Using the standard vaporizer (SV) installed in almost all commercial instruments, a collection efficiency (CE) correction, varying with aerosol phase and chemical composition, is needed to account for particle bounce losses. Recently, a new “capture vaporizer” (CV) has been shown to achieve CE∼1 for ambient aerosols, but its chemical detection properties show some differences from the SV due to the increased residence time of particles and vaporized molecules inside the CV. This study reports on the properties and changes of mass spectra of OA in CV-AMS using both AMS and ACSM for the first time. Compared with SV spectra, larger molecular-weight fragments tend to shift toward smaller ions in the CV due to additional thermal decomposition arising from increased residence time and hot surface collisions. Artifact CO⁺ ions (and to a lesser extent, H₂O⁺), when sampling long chain alkane/alkene-like OA (e.g., squalene) in the CV during the laboratory studies, are observed, probably caused by chemical reactions between sampled OA and molybdenum oxides on the vaporizer surfaces (with the carbon derived from the incident OA). No evidence for such CO⁺ enhancement is observed for ambient OA. Tracer ion marker fractions (f_m/z =, i.e., the ratio of the organic signal at a given m/z to the total OA signal), which are used to characterize the impact of different sources are still present and usable in the CV. A public, web-based spectral database for mass spectra from CV-AMS has been established. Copyright © 2018 American Association for Aerosol Research

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.