Detailed heterogeneous chemistry in an urban plume box model: reversible co-adsorption of O&amp;lt;sub&amp;gt;3&amp;lt;/sub&amp;gt;, NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;, and H&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;O on soot coated with benzo[a]pyrene

Springmann, M.; Knopf, Daniel A.; Riemer, Nicole

doi:10.5194/acp-9-7461-2009

Cited by 36 publications

(45 citation statements)

References 79 publications

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“…Longer half-lives in response to higher water vapour concentrations in the atmosphere were also observed by Springmann et al (2009) and can be explained by the large fraction of active surface sites that is covered by H 2 O molecules and thus unavailable for chemical reactions. Hence, in the high RH scenarios, less PAH is oxidised per unit time.…”

Section: Population Pah Half-lifementioning

confidence: 95%

“…Absolute values, however, differ quite strongly because Shiraiwa et al (2009) did not consider changes in gas phase composition, while Springmann et al (2009) simulated fewer heterogeneous reactions and used different values for some of the physico-chemical parameters.…”

Section: Individual Particlesmentioning

confidence: 99%

“…Subsequently, O 3 (s) and NO 2 (s) can undergo the surface layer reactions summarised in Table 2. Y j (j = 2,...,N nv ) are non-volatile oxidation and, possibly, nitration products of PAH whose exact chemical structure is not known (Springmann et al, 2009;Shiraiwa et al, 2009). H 2 O(s) does not react chemically in our scenarios.…”

Section: Simulation Parameters and Assumptionsmentioning

confidence: 99%

“…Springmann et al (2009) improved upon this by coupling the PRA mechanism to a gas phase chemical mechanism to account for changes in atmospheric gas phase composition due to the diurnal photochemical cycle and heterogeneous chemistry.…”

Section: Introductionmentioning

confidence: 99%

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Detailed heterogeneous oxidation of soot surfaces in a particle-resolved aerosol model

2011

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Abstract.Using the particle-resolved aerosol model PartMC-MOSAIC, we simulate the heterogeneous oxidation of a monolayer of polycyclic aromatic hydrocarbons (PAHs) on soot particles in an urban atmosphere. We focus on the interaction of the major atmospheric oxidants (O 3 , NO 2 , OH, and NO 3 ) with PAHs and include competitive co-adsorption of water vapour for a range of atmospheric conditions. For the first time detailed heterogeneous chemistry based on the Pöschl-Rudich-Ammann (PRA) framework is modelled on soot particles with a realistic size distribution and a continuous range of chemical ages. We find PAH half-lives, τ 1/2 , on the order of seconds during the night, when the PAHs are rapidly oxidised by the gas-surface reaction with NO 3 . During the day, τ 1/2 is on the order of minutes and determined mostly by the surface layer reaction of PAHs with adsorbed O 3 . Such short half-lives of surface-bound PAHs may lead to efficient conversion of hydrophobic soot into more hygroscopic particles, thus increasing the particles' aerosol-cloud interaction potential. Despite its high reactivity OH appears to have a negligible effect on PAH degradation which can be explained by its very low concentration in the atmosphere. An increase of relative humidity (RH) from 30 % to 80 % increases PAH half-lives by up to 50 % for daytime degradation and by up to 100 % or more for nighttime degradation. Uptake coefficients, averaged over the particle population, are found to be relatively constant over time for O 3 (∼ 2 × 10 −7 to ∼ 2×10 −6 ) and NO 2 (∼ 5×10 −6 to ∼ 10 −5 ) at the different levels of NO x emissions and RH considered in this study. In contrast, those for OH and NO 3 depend strongly on the surface concentration of PAHs. We do not find a significantCorrespondence to: N. Riemer (nriemer@illinois.edu) influence of heterogeneous reactions on soot particles on the gas phase composition. The derived half-lives of surfacebound PAHs and the time and particle population averaged uptake coefficients for O 3 and NO 2 presented in this paper can be used as parameterisations for the treatment of heterogeneous chemistry in large-scale atmospheric chemistry models.

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Section: Population Pah Half-lifementioning

confidence: 95%

Section: Individual Particlesmentioning

confidence: 99%

Section: Simulation Parameters and Assumptionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Detailed heterogeneous oxidation of soot surfaces in a particle-resolved aerosol model

2011

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“…Using K2-SURF Shiraiwa et al (2011b) showed that long-lived reactive oxygen intermediates are formed in the reaction of ozone with aerosol particles. Springmann et al (2009) and Kaiser et al (2011) demonstrated the applicability and usefulness of the PRA framework in an urban plume box model of the degradation of benzo [a]pyrene on soot by ozone and nitrogen dioxide. Pfrang et al (2010) developed a kinetic double-layer model coupling aerosol surface and bulk chemistry (K2-SUB), in which mass transport and chemical reactions in the bulk are not explicitly resolved but represented by a reacto-diffusive flux analogous to traditional resistormodel formulations.…”

mentioning

confidence: 99%

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

et al. 2012

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Abstract. We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KM-GAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KM-GAP is based on the PRA model framework (Pöschl-RudichAmmann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modeled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system and the computational constraints, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmospheric aerosols and clouds.In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at ∼270 K is close to unity (Winkler et al., 2006). Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for efficient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.

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Multiphase OH oxidation kinetics of organic aerosol: The role of particle phase state and relative humidity

Slade

Knopf

2014

Geophysical Research Letters

159

219

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Organic aerosol can exhibit different phase states in response to changes in relative humidity (RH), thereby influencing heterogeneous reaction rates with trace gas species. OH radical uptake by laboratory‐generated levoglucosan and methyl‐nitrocatechol particles, serving as surrogates for biomass burning aerosol, is determined as a function of RH. Increasing RH lowers the viscosity of amorphous levoglucosan aerosol particles enabling enhanced OH uptake. Conversely, OH uptake by methyl‐nitrocatechol aerosol particles is suppressed at higher RH as a result of competitive coadsorption of H2O that occupies reactive sites. This is shown to have substantial impacts on organic aerosol lifetimes with respect to OH oxidation. The results emphasize the importance of organic aerosol phase state to accurately describe the multiphase chemical kinetics and thus chemical aging process in atmospheric models to better represent the evolution of organic aerosol and its role in air quality and climate.

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Detailed heterogeneous chemistry in an urban plume box model: reversible co-adsorption of O<sub>3</sub>, NO<sub>2</sub>, and H<sub>2</sub>O on soot coated with benzo[a]pyrene

Cited by 36 publications

References 79 publications

Detailed heterogeneous oxidation of soot surfaces in a particle-resolved aerosol model

Detailed heterogeneous oxidation of soot surfaces in a particle-resolved aerosol model

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

Multiphase OH oxidation kinetics of organic aerosol: The role of particle phase state and relative humidity

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