CAMx–UNIPAR simulation of secondary organic aerosol mass formed from multiphase reactions of hydrocarbons under the Central Valley urban atmospheres of California

Abstract

Abstract. The UNIfied Partitioning-Aerosol phase Reaction (UNIPAR) model was integrated into the Comprehensive Air quality Model with extensions (CAMx) to process secondary organic aerosol (SOA) formation by capturing multiphase reactions of hydrocarbons (HCs) in regional scales. SOA growth was simulated using a wide range of anthropogenic HCs, including 10 aromatics and linear alkanes with different carbon lengths. The atmospheric processes of biogenic HCs (isoprene, terpenes, and sesquiterpene) were simulated for major oxidation paths (ozone, OH radicals, and nitrate radicals) to predict day and night SOA formation. The UNIPAR model streamlined the multiphase partitioning of the lumping species originating from semi-explicitly predicted gas products and their heterogeneous chemistry to form non-volatile oligomeric species in both organic aerosol and inorganic aqueous phase. The CAMx–UNIPAR model predicted SOA formation at four ground urban sites (San Jose, Sacramento, Fresno, and Bakersfield) in California, United States, during wintertime 2018. Overall, the simulated mass concentrations of the total organic matter, consisting of primary organic aerosol and SOA, showed a good agreement with the observations. The simulated SOA mass in the urban areas of California was predominated by alkane and terpene oxidation products. During the daytime, low-volatility products originating from the autoxidation of long-chain alkanes considerably contributed to the SOA mass. In contrast, a significant amount of nighttime SOA was produced by the reaction of terpene with ozone or nitrate radicals. The spatial distributions of anthropogenic SOA associated with aromatic and alkane HCs were noticeably affected by the southward wind direction, owing to the relatively long lifetime of their atmospheric oxidation, whereas those of biogenic SOA were nearly insensitive to wind direction. During wintertime 2018, the impact of inorganic aerosol hygroscopicity on the total SOA budget was not evident because of the small contribution of aromatic and isoprene products, which are hydrophilic and reactive in the inorganic aqueous phase. However, an increased isoprene SOA mass was predicted during the wet periods, although its contribution to the total SOA was little.

Formation and chemical evolution of SOA in two different environments: A dual chamber study

“…While developments, such as the volatility basis set (Donahue et al, 2011) and accounting for the intermediate volatility organic compounds (IVOCs), have significantly improved model predictions, the problem of underestimation often persists. For example, heterogeneous reactions that may affect SOA formation are not fully incorporated even in most recent models (Jo et al, 2024). Another reason for this underprediction is that models rely on measurements obtained from laboratory chamber experiments, that typically test the potential of individual VOCs to form SOA (Kroll and Seinfeld, 2008).…”