Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

Shiraiwa, Manabu; Pfrang, Christian; Koop, Thomas; Pöschl, Ulrich

doi:10.5194/acp-12-2777-2012

Cited by 193 publications

(278 citation statements)

References 89 publications

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“…Particle size has been discussed primarily in the context of accumulation mode particles greater than 100 nm in diameter (Roldin et al, 2014;Shiraiwa et al, 2013;Vesterinen et al, 2007). The Vesterinen study did report aerosol yield functions from simulations starting with 20 nm diameter seed particles, and the results suggested that particle-phase chemistry could enhance growth rates under atmospherically relevant conditions.…”

Section: Introductionmentioning

confidence: 91%

“…for constraining aerosol formation models. Future modeling of size-dependent molecular composition should include physico-chemical parameters such as diffusion, phase separation, and reaction reversibility (Liu et al, 2014;Mai et al, 2015;Riipinen et al, 2012;Shiraiwa et al, 2012;Song et al, 2015;Trump and Donahue, 2014;Zaveri et al, 2014) that may influence the contribution of particlephase chemistry to nanoparticle growth.…”

Section: Comparison To Recent Experimental Measurements and Atmosphermentioning

confidence: 99%

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Nanoparticle growth by particle-phase chemistry

Apsokardu¹,

Johnston²

2018

Atmos. Chem. Phys.

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Abstract. The ability of particle-phase chemistry to alter the molecular composition and enhance the growth rate of nanoparticles in the 2-100 nm diameter range is investigated through the use of a kinetic growth model. The molecular components included are sulfuric acid, ammonia, water, a non-volatile organic compound, and a semi-volatile organic compound. Molecular composition and growth rate are compared for particles that grow by partitioning alone vs. those that grow by a combination of partitioning and an accretion reaction in the particle phase between two organic molecules. Particle-phase chemistry causes a change in molecular composition that is particle diameter dependent, and when the reaction involves semi-volatile molecules, the particles grow faster than by partitioning alone. These effects are most pronounced for particles larger than about 20 nm in diameter. The modeling results provide a fundamental basis for understanding recent experimental measurements of the molecular composition of secondary organic aerosol showing that accretion reaction product formation increases linearly with increasing aerosol volume-to-surface-area. They also allow initial estimates of the reaction rate constants for these systems. For secondary aerosol produced by either OH oxidation of the cyclic dimethylsiloxane (D 5 ) or ozonolysis of β-pinene, oligomerization rate constants on the order of 10 −3 to 10 −1 M −1 s −1 are needed to explain the experimental results. These values are consistent with previously measured rate constants for reactions of hydroperoxides and/or peroxyacids in the condensed phase.

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Section: Introductionmentioning

confidence: 91%

Section: Comparison To Recent Experimental Measurements and Atmosphermentioning

confidence: 99%

Nanoparticle growth by particle-phase chemistry

Apsokardu¹,

Johnston²

2018

Atmos. Chem. Phys.

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“…The characteristic timescale to reach equilibrium partitioning can be estimated using the kinetic multi-layer model of gas-particle interactions (KM-GAP) 35 coupled with AIOMFAC. KM-GAP represents the particle phase with multiple compartments and layers, including a surface sorption layer and a number of bulk layers and treats gas-phase diffusion, reversible adsorption, and bulk diffusion explicitly (see Fig.…”

Section: Equilibration Timescale Of Soa Partitioningmentioning

confidence: 99%

Gas–particle partitioning of atmospheric aerosols: interplay of physical state, non-ideal mixing and morphology

Shiraiwa

Zuend

Bertram

et al. 2013

Phys. Chem. Chem. Phys.

251

268

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Atmospheric aerosols, comprising organic compounds and inorganic salts, play a key role in air quality and climate. Mounting evidence exists that these particles frequently exhibit phase separation into predominantly organic and aqueous electrolyte-rich phases. As well, the presence of amorphous semi-solid or glassy particle phases has been established. Using the canonical system of ammonium sulfate mixed with organics from the ozone oxidation of a-pinene, we illustrate theoretically the interplay of physical state, non-ideality, and particle morphology affecting aerosol mass concentration and the characteristic timescale of gas-particle mass transfer. Phase separation can significantly affect overall particle mass and chemical composition. Semi-solid or glassy phases can kinetically inhibit the partitioning of semivolatile components and hygroscopic growth, in contrast to the traditional assumption that organic compounds exist in quasi-instantaneous gas-particle equilibrium. These effects have significant implications for the interpretation of laboratory data and the development of improved atmospheric air quality and climate models.

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“…The "kinetic multi-layer model of gas-particle interactions in aerosol and clouds" (KM-GAP) (Shiraiwa et al, 2012), based on coupled differential equations;…”

Section: S O'meara Et Al: the Rate Of Equilibration Of Viscous Aeromentioning

confidence: 99%

The rate of equilibration of viscous aerosol particles

2016

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Abstract. The proximity of atmospheric aerosol particles to equilibrium with their surrounding condensable vapours can substantially impact their transformations, fate and impacts and is the subject of vibrant research activity. In this study we first compare equilibration timescales estimated by three different models for diffusion through aerosol particles to assess any sensitivity to choice of model framework. Equilibration times for diffusion coefficients with varying dependencies on composition are compared for the first time. We show that even under large changes in the saturation ratio of a semivolatile component (e s ) of 1-90 % predicted equilibration timescales are in agreement, including when diffusion coefficients vary with composition. For condensing water and a diffusion coefficient dependent on composition, a plasticising effect is observed, leading to a decreased estimated equilibration time with increasing final e s . Above 60 % final e s maximum equilibration times of around 1 s are estimated for comparatively large particles (10 µm) containing a relatively low diffusivity component (1 × 10 −25 m 2 s −1 in pure form). This, as well as other results here, questions whether particlephase diffusion through water-soluble particles can limit hygroscopic growth in the ambient atmosphere. In the second part of this study, we explore sensitivities associated with the use of particle radius measurements to infer diffusion coefficient dependencies on composition using a diffusion model. Given quantified similarities between models used in this study, our results confirm considerations that must be taken into account when designing such experiments. Although quantitative agreement of equilibration timescales between models is found, further work is necessary to determine their suitability for assessing atmospheric impacts, such as their inclusion in polydisperse aerosol simulations.

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Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

Cited by 193 publications

References 89 publications

Nanoparticle growth by particle-phase chemistry

Nanoparticle growth by particle-phase chemistry

Gas–particle partitioning of atmospheric aerosols: interplay of physical state, non-ideal mixing and morphology

The rate of equilibration of viscous aerosol particles

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