Abstract. Volatility and viscosity are important properties of organic aerosols (OA),affecting aerosol processes such as formation, evolution, and partitioning ofOA. Volatility distributions of ambient OA particles have often beenmeasured, while viscosity measurements are scarce. We have previouslydeveloped a method to estimate the glass transition temperature (Tg) ofan organic compound containing carbon, hydrogen, and oxygen. Based onanalysis of over 2400 organic compounds including oxygenated organiccompounds, as well as nitrogen- and sulfur-containing organic compounds, weextend this method to include nitrogen- and sulfur-containing compoundsbased on elemental composition. In addition, parameterizations are developedto predict Tg as a function of volatility and the atomicoxygen-to-carbon ratio based on a negative correlation between Tg andvolatility. This prediction method of Tg is applied to ambientobservations of volatility distributions at 11 field sites. Thepredicted Tg values of OA under dry conditions vary mainly from 290 to 339 Kand the predicted viscosities are consistent with the results of ambientparticle-phase-state measurements in the southeastern US and the Amazonianrain forest. Reducing the uncertainties in measured volatility distributionswould improve predictions of viscosity, especially at low relative humidity.We also predict the Tg of OA components identified via positive matrixfactorization of aerosol mass spectrometer (AMS) data. The predicted viscosity ofoxidized OA is consistent with previously reported viscosity of secondary organic aerosols (SOA) derivedfrom α-pinene, toluene, isoprene epoxydiol (IEPOX), and diesel fuel.Comparison of the predicted viscosity based on the observed volatilitydistributions with the viscosity simulated by a chemical transport modelimplies that missing low volatility compounds in a global model can lead tounderestimation of OA viscosity at some sites. The relation betweenvolatility and viscosity can be applied in the molecular corridor orvolatility basis set approaches to improve OA simulations in chemicaltransport models by consideration of effects of particle viscosity in OAformation and evolution.
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Optimization of process models for determining volatility distribution and viscosity of organic aerosols from isothermal particle evaporation data
Abstract. The composition of organic aerosol under different ambient conditions aswell as their phase state have been a subject of intense study in recentyears. One way to study particle properties is to measure the particlesize shrinkage in a diluted environment at isothermal conditions. From thesemeasurements it is possible to separate the fraction of low-volatilitycompounds from high-volatility compounds. In this work, we analyse andevaluate a method for obtaining particle composition and viscosity frommeasurements using process models coupled with input optimizationalgorithms. Two optimization methods, the Monte Carlo genetic algorithm andBayesian inference, are used together with process models describing thedynamics of particle evaporation. The process model optimization scheme ininferring particle composition in a volatility-basis-set sense andcomposition-dependent particle viscosity is tested with artificiallygenerated data sets and real experimental data. Optimizing model input sothat the output matches these data yields a good match for the estimatedquantities. Both optimization methods give equally good results when theyare used to estimate particle composition to artificially test data. The timescale of the experiments and the initial particle size are found to beimportant in defining the range of values that can be identified for theproperties from the optimization.
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- Award ID(s):
- 1654104
- PAR ID:
- 10142828
- Date Published:
- Journal Name:
- Atmospheric Chemistry and Physics
- Volume:
- 19
- Issue:
- 14
- ISSN:
- 1680-7324
- Page Range / eLocation ID:
- 9333 to 9350
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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