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Atmospheric Chemistry and Physics An interactive open-access journal of the European Geosciences Union
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© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.

  07 Oct 2020

07 Oct 2020

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This preprint is currently under review for the journal ACP.

Non-equilibrium interplay between gas-particle partitioning and multiphase chemical reactions of semi-volatile compounds: mechanistic insights and practical implications for atmospheric modeling of PAHs

Jake Wilson1, Ulrich Pöschl1, Manabu Shiraiwa2, and Thomas Berkemeier1 Jake Wilson et al.
  • 1Multiphase Chemistry Department, Max Planck Institute for Chemistry, Mainz, Germany
  • 2Department of Chemistry, University of California, Irvine, CA, USA

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 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 ≈ 1/(kdes + 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 PAHs 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 explicit-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 are not only 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.

Jake Wilson et al.

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Jake Wilson et al.

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Publications Copernicus
Short summary
This work explores the gas-particle partitioning of PAHs on soot with a kinetic model. We show that the equilibration timescale depends on PAH molecular structure, temperature and particle number concentration and either adsorption or desorption can be the controlling process. We explore scenarios in which the particulate fraction is perturbed from equilibrium by chemical loss and discuss implications for chemical transport models that assume instantaneous equilibration at each model time step.
This work explores the gas-particle partitioning of PAHs on soot with a kinetic model. We show...