Development of a multiphase chemical mechanism to improve secondary organic aerosol formation in CAABA/MECCA (version 4.5.6-rc.1)

Abstract

Abstract. During the last decades, the impact of multiphase chemistry on secondary organic aerosol (SOA) has been demonstrated to be key in explaining lab experiments and field measurements. However, global atmospheric models still show large biases when simulating atmospheric observations of organic aerosols (OA). Major reasons for the model errors are the use of simplified chemistry schemes of gas-phase oxidation of vapors and parameterization of heterogeneous surface reactions. The photochemical oxidation of anthropogenic and biogenic volatile organic compounds (VOC) leads to products that either produce new SOA or are taken up by existing aqueous media like cloud droplets and deliquescent aerosols. After partitioning, aqueous-phase processing results in polyols, organosulfates, and other products with a high molar mass and oxygen content. In this work, we have introduced the formation of new low-volatility organic compounds (LVOC) into the multiphase chemistry box model CAABA/MECCA. Most notable is the addition of the SOA precursors limonene, long-chain alkanes (up to 8 C atoms), and a semi-explicit chemical mechanism for the formation of LVOC from isoprene oxidation in the gas- and aqueous-phase. Moreover, Henry’s law solubility constants and their temperature dependences have been estimated for the partitioning of organic molecules to the aqueous phase. Box model simulations indicate that the new chemical scheme predicts enhanced formation of LVOC, which are accounted for being precursor species to SOA. As expected, the model predicts that LVOC is positively correlated to temperature but negatively correlated to NOx levels. However, the aqueous-phase processing of isoprene-epoxydiols (IEPOX) displays a more complex dependence on these two key variables. Semi-quantitative comparison with observations from the SOAS campaign suggests that the model may overestimate methylbutane-1,2,3,4-tetrol (MeBuTETROL) from IEPOX. The extensions in CAABA/MECCA will be ported to the 3D-atmospheric model MESSy for a comprehensive evaluation of the impact of aqueous-phase chemistry on SOA at a global scale.

How non-equilibrium aerosol chemistry impacts particle acidity: the GMXe AERosol CHEMistry (GMXe–AERCHEM, v1.0) sub-submodel of MESSy

“…CC BY 4.0 License. stable organo sulfates (Eddingsaas et al, 2010;Wieser et al, 2023). An insignificant difference between simulated values of ISORROPIA-II and AERCHEM is observed in the Midwest.…”

“…With the implementation of AERCHEM, we can now overcome these technical constraints and explicitly represent SOA formation arising from aqueous-phase processes. This expansion is not limited to glyoxal and methylglyoxal but may also encompass other precursors like isoprene-epoxydiols (IEPOX), recently developed for the MESSy submodel MECCA by Wieser et al (2023). By incorporating these advanced representations, MESSy gains improved accuracy and comprehensiveness in capturing atmospheric SOA formation.…”