The prediction of Secondary Organic Aerosol (SOA) in regional scales is traditionally performed by using gas-particle partitioning models. In the presence of inorganic salted wet aerosols, aqueous reactions of semivolatile organic compounds can also significantly contribute to SOA formation. The UNIfied Partitioning-Aerosol phase Reaction (UNIPAR) model utilizes the explicit gas mechanism to better predict SOA formation from multiphase reactions of hydrocarbons. In this work, the UNIPAR model was incorporated with the Comprehensive Air Quality Model with Extensions (CAMx) to predict the ambient concentration of organic matter (OM) in urban atmospheres during the Korean-United States Air Quality (2016 KORUS-AQ) campaign. The SOA mass predicted with the CAMx-UNIPAR model changed with varying levels of humidity and emissions and in turn, has the potential to improve the accuracy of OM simulations. The CAMx-UNIPAR model significantly improved the simulation of SOA formation under the wet condition, which often occurred during the KORUS-AQ campaign, through the consideration of aqueous reactions of reactive organic species and gas-aqueous partitioning. The contribution of aromatic SOA to total OM was significant during the low-level transport/haze period (24-31 May 2016) because aromatic oxygenated products are hydrophilic and reactive in aqueous aerosols. The OM mass predicted with the CAMx-UNIPAR model was compared with that predicted with the CAMx model integrated with the conventional two product model (SOAP). Based on estimated statistical parameters to predict OM mass, the performance of CAMx-UNIPAR was noticeably better than the conventional CAMx model although both SOA models underestimated OM compared to observed values, possibly due to missing precursor hydrocarbons such as sesquiterpenes, alkanes, and intermediate VOCs. The CAMx-UNIPAR model simulation suggested that in the urban areas of South Korea, terpene and anthropogenic emissions significantly contribute to SOA formation while isoprene SOA minimally impacts SOA formation.
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Gas–particle partitioning of polyol tracers at a suburban site in Nanjing, east China: increased partitioning to the particle phase
Abstract. Gas–particle partitioning of water-soluble organic compounds plays a significant role in influencing the formation, transport, and lifetime oforganic aerosols in the atmosphere, but is poorly characterized. In this work, gas- and particle-phase concentrations of isoprene oxidation products(C5-alkene triols and 2-methylterols), levoglucosan, and sugar polyols were measured simultaneously at a suburban site of the western Yangtze RiverDelta in east China. All target polyols were primarily distributed into the particle phase (85.9 %–99.8 %). Given the uncertainties inmeasurements and vapor pressure predictions, a dependence of particle-phase fractions on vapor pressures cannot be determined. To explore the impactof aerosol liquid water on gas–particle partitioning of polyol tracers, three partitioning schemes (Cases 1–3) were proposed based onequilibriums of gas vs. organic and aqueous phases in aerosols. If particulate organic matter (OM) is presumed as the only absorbing phase(Case 1), the measurement-based absorptive partitioning coefficients (Kp,OMm) of isoprene oxidation products and levoglucosan were more than 10 times greater than predicted values (Kp,OMt). The agreement betweenKp,OMm and Kp,OMt was substantially improved when solubility in a separate aqueous phase wasincluded, whenever water-soluble and water-insoluble OM partitioned into separate (Case 2) or single (Case 3) liquid phases,suggesting that the partitioning of polyol tracers into the aqueous phase in aerosols should not be ignored. The measurement-based effective Henry'slaw coefficients (KH,em) of polyol tracers were orders of magnitude higher than their predicted values in pure water(KH,wt). Due to the moderate correlations between log(KH,em/KH,wt) andmolality of sulfate ions, the gap between KH,em and KH,wt of polyol tracers could not be fullyparameterized by the equation defining “salting-in” effects and might be ascribed to mechanisms of reactive uptake, aqueous phase reaction,“like-dissolves-like” principle, etc. These study results also partly reveal the discrepancy between observation and modeling of organicaerosols.
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- Award ID(s):
- 1743401
- PAR ID:
- 10315320
- Date Published:
- Journal Name:
- Atmospheric Chemistry and Physics
- Volume:
- 21
- Issue:
- 15
- ISSN:
- 1680-7324
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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