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Abstract. Secondary organic aerosols (SOA) are major components of atmospheric fineparticulate matter, affecting climate and air quality. Mounting evidenceexists that SOA can adopt glassy and viscous semisolid states, impactingformation and partitioning of SOA. In this study, we apply the GECKO-A(Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere)model to conduct explicit chemical modeling of isoprene photooxidation andα-pinene ozonolysis and their subsequent SOA formation. The detailedgas-phase chemical schemes from GECKO-A are implemented into a box model andcoupled to our recently developed glass transition temperatureparameterizations, allowing us to predict SOA viscosity. The effects ofchemical composition, relative humidity, mass loadings and mass accommodation on particle viscosity are investigated in comparison withmeasurements of SOA viscosity. The simulated viscosity of isoprene SOAagrees well with viscosity measurements as a function of relative humidity,while the model underestimates viscosity of α-pinene SOA by a feworders of magnitude. This difference may be due to missing processes in themodel, including autoxidation and particle-phase reactions, leading to theformation of high-molar-mass compounds that would increase particleviscosity. Additional simulations imply that kinetic limitations of bulkdiffusion and reduction in mass accommodation coefficient may play a role inenhancing particle viscosity by suppressing condensation of semi-volatilecompounds. The developed model is a useful tool for analysis andinvestigation of the interplay among gas-phase reactions, particle chemicalcomposition and SOA phase state.
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The Influence of Absolute Mass Loading of Secondary Organic Aerosols on Their Phase State
Absolute secondary organic aerosol (SOA) mass loading (CSOA) is a key parameter in determining partitioning of semi- and intermediate volatility compounds to the particle phase. Its impact on the phase state of SOA, however, has remained largely unexplored. In this study, systematic laboratory chamber measurements were performed to elucidate the influence of CSOA, ranging from 0.2 to 160 µg m−3, on the phase state of SOA formed by ozonolysis of various precursors, including α-pinene, limonene, cis-3-hexenyl acetate (CHA) and cis-3-hexen-1-ol (HXL). A previously established method to estimate SOA bounce factor (BF, a surrogate for particle viscosity) was utilized to infer particle viscosity as a function of CSOA. Results show that under nominally identical conditions, the maximum BF decreases by approximately 30% at higher CSOA, suggesting a more liquid phase state. With the exception of HXL-SOA (which acted as the negative control), the phase state for all studied SOA precursors varied as a function of CSOA. Furthermore, the BF was found to be the maximum when SOA particle distributions reached a geometric mean particle diameter of 50–60 nm. Experimental results indicate that CSOA is an important parameter impacting the phase state of SOA, reinforcing recent findings that extrapolation of experiments not conducted at atmospherically relevant SOA levels may not yield results that are relevant to the natural environment.
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- Award ID(s):
- 1709751
- PAR ID:
- 10105139
- Date Published:
- Journal Name:
- Atmosphere
- Volume:
- 9
- Issue:
- 4
- ISSN:
- 2073-4433
- Page Range / eLocation ID:
- 131
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/atmos9040131
