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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Mass accommodation and gas–particle partitioning in secondary organic aerosols: dependence on diffusivity, volatility, particle-phase reactions, and penetration depth
Abstract. Mass accommodation is an essential process for gas–particle partitioning oforganic compounds in secondary organic aerosols (SOA). The massaccommodation coefficient is commonly described as the probability of a gasmolecule colliding with the surface to enter the particle phase. It is oftenapplied, however, without specifying if and how deep a molecule has topenetrate beneath the surface to be regarded as being incorporated into thecondensed phase (adsorption vs. absorption). While this aspect is usuallynot critical for liquid particles with rapid surface–bulk exchange, it canbe important for viscous semi-solid or glassy solid particles to distinguishand resolve the kinetics of accommodation at the surface, transfer acrossthe gas–particle interface, and further transport into the particle bulk. For this purpose, we introduce a novel parameter: an effective massaccommodation coefficient αeff that depends on penetrationdepth and is a function of surface accommodation coefficient, volatility,bulk diffusivity, and particle-phase reaction rate coefficient. Applicationof αeff in the traditional Fuchs–Sutugin approximation ofmass-transport kinetics at the gas–particle interface yields SOApartitioning results that are consistent with a detailed kinetic multilayermodel (kinetic multilayer model of gas–particle interactions in aerosols and clouds, KM-GAP; Shiraiwa et al., 2012) and two-film model solutions (Modelfor Simulating Aerosol Interactions and Chemistry, MOSAIC;Zaveri et al., 2014) but deviate substantially from earlier modelingapproaches not considering the influence of penetration depth and relatedparameters. For highly viscous or semi-solid particles, we show that the effective massaccommodation coefficient remains similar to the surface accommodationcoefficient in the case of low-volatility compounds, whereas it can decrease byseveral orders of magnitude in the case of semi-volatile compounds. Such effectscan explain apparent inconsistencies between earlier studies deriving massaccommodation coefficients from experimental data or from molecular dynamicssimulations. Our findings challenge the approach of traditional SOA models using theFuchs–Sutugin approximation of mass transfer kinetics with a fixed massaccommodation coefficient, regardless of particle phase state and penetrationdepth. The effective mass accommodation coefficient introduced in this studyprovides an efficient new way of accounting for the influence of volatility,diffusivity, and particle-phase reactions on SOA partitioning in processmodels as well as in regional and global air quality models. While kineticlimitations may not be critical for partitioning into liquid SOA particlesin the planetary boundary layer (PBL), the effects are likely important foramorphous semi-solid or glassy SOA in the free and upper troposphere (FT–UT)as well as in the PBL at low relative humidity and low temperature.
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- Award ID(s):
- 1654104
- NSF-PAR ID:
- 10252228
- Date Published:
- Journal Name:
- Atmospheric Chemistry and Physics
- Volume:
- 21
- Issue:
- 3
- ISSN:
- 1680-7324
- Page Range / eLocation ID:
- 1565 to 1580
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.5194/acp-21-1565-2021
