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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Non-equilibrium interplay between gas–particle partitioning and multiphase chemical reactions of semi-volatile compounds: mechanistic insights and practical implications for atmospheric modeling of polycyclic aromatic hydrocarbons
Abstract. Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic air pollutants. The dispersion of PAHs in the atmosphere is influenced by gas–particle partitioning and chemical loss. These processes are closely interlinked and may occur at vastly differing timescales, which complicates their mathematical description in chemical transport models. Here, we use a kinetic model that explicitly resolves mass transport and chemical reactions in the gas and particle phases to describe and explore the dynamic and non-equilibrium interplay of gas–particle partitioning and chemical losses of PAHs on soot particles. We define the equilibration timescale τeq of gas–particle partitioning as the e-folding time for relaxation of the system to the partitioning equilibrium. We find this metric to span from seconds to hours depending on temperature, particle surface area, and the type of PAH. The equilibration time can be approximated using a time-independent equation, τeq≈1kdes+kads, which depends on the desorption rate coefficient kdes and adsorption rate coefficient kads, both of which can be calculated from experimentally accessible parameters. The model reveals two regimes in which different physical processes control the equilibration timescale: a desorption-controlled and an adsorption-controlled regime. In a case study with the PAH pyrene, we illustrate how chemical loss can perturb the equilibrium particulate fraction at typical atmospheric concentrations of O3 and OH. For the surface reaction with O3, the perturbation is significant and increases with the gas-phase concentration of O3. Conversely, perturbations are smaller for reaction with the OH radical, which reacts with pyrene on both the surface of particles and in the gas phase. Global and regional chemical transport models typically approximate gas–particle partitioning with instantaneous-equilibration approaches. We highlight scenarios in which these approximations deviate from the explicitly coupled treatment of gas–particle partitioning and chemistry presented in this study. We find that the discrepancy between solutions depends on the operator-splitting time step and the choice of time step can help to minimize the discrepancy. The findings and techniques presented in this work not only are relevant for PAHs but can also be applied to other semi-volatile substances that undergo chemical reactions and mass transport between the gas and particle phase.
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- Award ID(s):
- 1654104
- NSF-PAR ID:
- 10252229
- Date Published:
- Journal Name:
- Atmospheric Chemistry and Physics
- Volume:
- 21
- Issue:
- 8
- ISSN:
- 1680-7324
- Page Range / eLocation ID:
- 6175 to 6198
- 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-21-6175-2021
