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Abstract. Evidence has accumulated that secondary organic aerosols (SOAs) exhibit complex morphologies with multiple phases that can adopt amorphous semisolid or glassy phase states. However, experimental analysis and numerical modeling on the formation and evolution of SOA still often employ equilibrium partitioning with an ideal mixing assumption in the particle phase. Here we apply the kinetic multilayer model of gas–particle partitioning (KM-GAP) to simulate condensation of semi-volatile species into a core–shell phase-separated particle to evaluate equilibration timescales of SOA partitioning. By varying bulk diffusivity and the activity coefficient of the condensing species in the shell, we probe the complex interplay of mass transfer kinetics and the thermodynamics of partitioning. We found that the interplay of non-ideality and phase state can impact SOA partitioning kinetics significantly. The effect of non-ideality on SOA partitioning is slight for liquid particles but becomes prominent in semisolid or solid particles. If the condensing species is miscible with a low activity coefficient in the viscous shell phase, the particle can reach equilibrium with the gas phase long before the dissolution of concentration gradients in the particle bulk. For the condensation of immiscible species with a high activity coefficient in the semisolid shell, the mass concentration in the shell may become higher or overshoot its equilibrium concentration due to slow bulk diffusion through the viscous shell for excess mass to be transferred to the core phase. Equilibration timescales are shorter for the condensation of lower-volatility species into semisolid shell; as the volatility increases, re-evaporation becomes significant as desorption is faster for volatile species than bulk diffusion in a semisolid matrix, leading to an increase in equilibration timescale. We also show that the equilibration timescale is longer in an open system relative to a closed system especially for partitioning of miscible species; hence, caution should be exercised when interpreting and extrapolating closed-system chamber experimental results to atmosphere conditions. Our results provide a possible explanation for discrepancies between experimental observations of fast particle–particle mixing and predictions of long mixing timescales in viscous particles and provide useful insights into description and treatment of SOA in aerosol models.
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Single-particle experiments measuring humidity and inorganic salt effects on gas-particle partitioning of butenedial
Abstract. An improved understanding of the fate and properties of atmospheric aerosolparticles requires a detailed process-level understanding of fundamentalfactors influencing the aerosol, including partitioning of aerosolcomponents between the gas and particle phases. Laboratory experiments withlevitated particles provide a way to study fundamental aerosol processesover timescales relevant to the multiday lifetime of atmospheric aerosolparticles, in a controlled environment in which various characteristicsrelevant to atmospheric aerosol can be prepared (e.g., highsurface-to-volume ratio, highly concentrated or supersaturated solutions,changes to relative humidity). In this study, the four-carbon unsaturatedcompound butenedial, a dialdehyde produced by oxidation of aromaticcompounds that undergoes hydration in the presence of water, was used as amodel organic aerosol component to investigate different factors affectinggas–particle partitioning, including the role of lower-volatility“reservoir” species such as hydrates, timescales involved inequilibration between higher- and lower-volatility forms, and the effect ofinorganic salts. The experimental approach was to use a laboratory systemcoupling particle levitation in an electrodynamic balance (EDB) withparticle composition measurement via mass spectrometry (MS). In particular,by fitting measured evaporation rates to a kinetic model, the effectivevapor pressure was determined for butenedial and compared under differentexperimental conditions, including as a function of ambient relativehumidity and the presence of high concentrations of inorganic salts. Even underdry (RH<5 %) conditions, the evaporation rate of butenedial isorders of magnitude lower than what would be expected if butenedial existedpurely as a dialdehyde in the particle, implying an equilibrium stronglyfavoring hydrated forms and the strong preference of certain dialdehydecompounds to remain in a hydrated form even under lower water contentconditions. Butenedial exhibits a salting-out effect in the presence ofsodium chloride and sodium sulfate, in contrast to glyoxal. The outcomes ofthese experiments are also helpful in guiding the design of future EDB-MSexperiments.
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- Award ID(s):
- 1808084
- PAR ID:
- 10176966
- Date Published:
- Journal Name:
- Atmospheric Chemistry and Physics
- Volume:
- 19
- Issue:
- 22
- ISSN:
- 1680-7324
- Page Range / eLocation ID:
- 14195 to 14209
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.5194/acp-19-14195-2019
