Diffusion of Organic Molecules as a Function of Temperature in a Sucrose Matrix (a Proxy for Secondary Organic Aerosol)

Kiland, Kristian J.; Maclean, Adrian M.; Kamal, Saeid; Bertram, Allan K.

doi:10.1021/acs.jpclett.9b02182

Cited by 18 publications

(26 citation statements)

References 87 publications

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“…Our results are consistent with previous studies reporting the significance of particle phase state for the reactive uptake kinetics (Arangio et al, 2015;Knopf et al, 2005;Kolesar et al, 2014;Slade and Knopf, 2014;Davies and Wilson, 2015;. To resolve the molecular processes of the measured heterogeneous kinetics, detailed modelling studies (Pöschl et al, 2007;Shiraiwa et al, 2010;Arangio et al, 2015;Houle et al, 2015;Houle et al, 2018;Pöschl and Shiraiwa, 2015) extended to lower temperatures are needed.…”

Section: Discussionsupporting

confidence: 91%

“…As has been demonstrated for heterogeneous ozonolysis reactions, the composition of the condensed phase can alter the phase state, thereby, significantly altering the reactive uptake kinetics (Knopf et al, 2005;Hearn et al, 2005;de Gouw and Lovejoy, 1998;Ziemann, 2005). In general, the solid condensed phase showed significantly lower γ O 3 values compared to the ozonolysis of the liquid phase.…”

Section: Introductionmentioning

confidence: 80%

“…The experimental system is based on our previous setups (Slade and Knopf, 2013;Knopf et al, 2005) and includes a temperature-controlled coated-wall flow reactor and a custom-built chemical ionization mass spectrometer (CIMS), as shown in Fig. 1.…”

Section: Apparatusmentioning

confidence: 99%

“…The phase state of OA can be modulated by particle composition and environmental conditions such as relative humidity (RH) and temperature (Koop et al, 2011;Zobrist et al, 2008;Shiraiwa et al, 2017a;Petters et al, 2019). Particle viscosity will influence the diffusion of atmospheric oxidants and other small gas molecules (e.g., O 3 , OH, NO 3 , H 2 O) entering the organic matrix (Price et al, 2015;Zobrist et al, 2011;Slade et al, 2017;Davies and Wilson, 2016;Moridnejad and Preston, 2016) as well as the transport and mixing of the condensed-phase organic species (Rothfuss and Petters, 2017;Marsh et al, 2018;Lienhard et al, 2015;Abramson et al, 2013;Chenyakin et al, 2017;Kiland et al, 2019). Therefore, it can be expected that the particle phase state will significantly affect the rate of multiphase chemical kinetics (Shiraiwa and Seinfeld, 2012;Slade and Knopf, 2014;Kolesar et al, 2014;Knopf et al, 2005;Katrib et al, 2005a;Davies and Wilson, 2015;Pöschl and Shiraiwa, 2015).…”

Section: Introductionmentioning

confidence: 99%

“…The temperature in the troposphere ranges approximately from 200 K to 300 K (Wallace and Hobbs, 2006), with subsequent impact on the OA phase state (Shiraiwa et al, 2017a;Koop et al, 2011) and multiphase reaction kinetics. However, only a few laboratory studies investigated the temperature dependence of heterogeneous oxidation reactions while considering the phase transition of organic substrates and aerosol particles (de Gouw and Lovejoy, 1998;Edebeli et al, 2019;Knopf et al, 2005;Slade et al, 2017;Moise and Rudich, 2000;. demonstrated that the uptake of ozone by oleic and linoleic acid is a strong function of temperature, where γ decreases by about an order of magnitude with decreasing temperature when both substrates transformed from a liquid to a solid state.…”

Section: Introductionmentioning

confidence: 99%

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Heterogeneous oxidation of amorphous organic aerosol surrogates by O3, NO3, and OH at typical tropospheric temperatures

Li¹,

Forrester²,

Knopf³

2020

Preprint

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Abstract. Typical tropospheric temperatures render possible phase states of amorphous organic aerosol (OA) particles to solid, semi-solid and liquid. This will affect the multiphase oxidation kinetics involving the organic condensed phase and gaseous oxidants and radicals. To quantify this effect, we determined the reactive uptake coefficients (&#947;) of O3, NO3 and OH by substrate films composed of single and binary OA surrogate species under dry conditions for temperatures from 213 to 313&#8201;K. A temperature-controlled coated-wall flow reactor coupled to a chemical ionization mass spectrometer was applied to determine &#947; with consideration of gas diffusion transport limitation and gas flow entrance effects, which can impact heterogeneous reaction kinetics. The phase state of the organic substrates was probed via the poke-flow technique, allowing the estimation of the substrates&#8217; glass transition temperatures. &#947; values for O3 and OH uptake to a canola oil substrate, NO3 uptake to a levoglucosan and a levoglucosan/xylitol substrate, and OH uptake to a glucose and glucose/1,2,6-hexanetriol substrate have been determined as a function of temperature. We observed the greatest changes in &#947; with temperature for substrates that experienced the largest changes in viscosity as a result of a solid-to-liquid phase transition. Organic substrates that maintain a semi-solid or solid phase state and as such a relatively higher viscosity, do not display large variations in heterogeneous reactivity. From 213&#8201;K to 293&#8201;K, &#947; values of O3 with canola oil, of NO3 with a levoglucosan/xylitol mixture, and of OH with a glucose/1,2,6-hexanetriol mixture and canola oil, increase by about a factor of 34, 3, 2 and 5, respectively, due to a solid-to-liquid phase transition of the substrate. These results demonstrate that the surface and bulk lifetime of the OA surrogate species can significantly increase due to the slowed heterogeneous kinetics when OA species are solid or highly viscous in the middle and upper troposphere. This experimental study will further our understanding of the chemical evolution of OA particles with subsequent important consequences for source apportionment, air quality, and climate.

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Section: Discussionsupporting

confidence: 91%

Section: Introductionmentioning

confidence: 80%

Section: Apparatusmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Heterogeneous oxidation of amorphous organic aerosol surrogates by O3, NO3, and OH at typical tropospheric temperatures

Li¹,

Forrester²,

Knopf³

2020

Preprint

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Photochemical Degradation of 4-Nitrocatechol and 2,4-Dinitrophenol in a Sugar-Glass Secondary Organic Aerosol Surrogate

Dalton

Nizkorodov

2021

Environ. Sci. Technol.

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The roles that chemical environment and viscosity play in the photochemical fate of molecules trapped in atmospheric particles are poorly understood. The goal of this work was to characterize the photolysis of 4-nitrocatechol (4NC) and 2,4dinitrophenol (24DNP) in semisolid isomalt as a new type of surrogate for glassy organic aerosols and compare it to photolysis in liquid water, isopropanol, and octanol. UV/vis spectroscopy was used to monitor the absorbance decay to determine the rates of photochemical loss of 4NC and 24DNP. The quantum yield of 4NC photolysis was found to be smaller in an isomalt glass (2.6 × 10 −6 ) than in liquid isopropanol (1.1 × 10 −5 ). Both 4NC and 24NDP had much lower photolysis rates in water than in organic matrices, suggesting that they would photolyze more efficiently in organic aerosol particles than in cloud or fog droplets. Liquid chromatography in tandem with mass spectrometry was used to examine the photolysis products of 4NC. In isopropanol solution, most products appeared to result from the oxidation of 4NC, in stark contrast to photoreduction and dimerization products that were observed in solid isomalt. Therefore, the photochemical fate of 4NC, and presumably of other nitrophenols, should depend on whether they undergo photodegradation in a liquid or semisolid organic particle.

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Phase Behavior and Viscosity in Biomass Burning Organic Aerosol and Climatic Impacts

Gregson,

Gerrebos,

Schervish

et al. 2023

Environ. Sci. Technol.

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Smoke particles generated by burning biomass consist mainly of organic aerosol termed biomass burning organic aerosol (BBOA). BBOA influences the climate by scattering and absorbing solar radiation or acting as nuclei for cloud formation. The viscosity and the phase behavior (i.e., the number and type of phases present in a particle) are properties of BBOA that are expected to impact several climate-relevant processes but remain highly uncertain. We studied the phase behavior of BBOA using fluorescence microscopy and showed that BBOA particles comprise two organic phases (a hydrophobic and a hydrophilic phase) across a wide range of atmospheric relative humidity (RH). We determined the viscosity of the two phases at room temperature using a photobleaching method and showed that the two phases possess different RH-dependent viscosities. The viscosity of the hydrophobic phase is largely independent of the RH from 0 to 95%. We use the Vogel–Fulcher–Tamman equation to extrapolate our results to colder and warmer temperatures, and based on the extrapolation, the hydrophobic phase is predicted to be glassy (viscosity >1012 Pa s) for temperatures less than 230 K and RHs below 95%, with possible implications for heterogeneous reaction kinetics and cloud formation in the atmosphere. Using a kinetic multilayer model (KM-GAP), we investigated the effect of two phases on the atmospheric lifetime of brown carbon within BBOA, which is a climate-warming agent. We showed that the presence of two phases can increase the lifetime of brown carbon in the planetary boundary layer and polar regions compared to previous modeling studies. Hence, the presence of two phases can lead to an increase in the predicted warming effect of BBOA on the climate.

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Diffusion of Organic Molecules as a Function of Temperature in a Sucrose Matrix (a Proxy for Secondary Organic Aerosol)

Cited by 18 publications

References 87 publications

Heterogeneous oxidation of amorphous organic aerosol surrogates by O<sub>3</sub>, NO<sub>3</sub>, and OH at typical tropospheric temperatures

Heterogeneous oxidation of amorphous organic aerosol surrogates by O<sub>3</sub>, NO<sub>3</sub>, and OH at typical tropospheric temperatures

Photochemical Degradation of 4-Nitrocatechol and 2,4-Dinitrophenol in a Sugar-Glass Secondary Organic Aerosol Surrogate

Phase Behavior and Viscosity in Biomass Burning Organic Aerosol and Climatic Impacts

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Diffusion of Organic Molecules as a Function of Temperature in a Sucrose Matrix (a Proxy for Secondary Organic Aerosol)

Cited by 18 publications

References 87 publications

Heterogeneous oxidation of amorphous organic aerosol surrogates by O&lt;sub&gt;3&lt;/sub&gt;, NO&lt;sub&gt;3&lt;/sub&gt;, and OH at typical tropospheric temperatures

Heterogeneous oxidation of amorphous organic aerosol surrogates by O&lt;sub&gt;3&lt;/sub&gt;, NO&lt;sub&gt;3&lt;/sub&gt;, and OH at typical tropospheric temperatures

Photochemical Degradation of 4-Nitrocatechol and 2,4-Dinitrophenol in a Sugar-Glass Secondary Organic Aerosol Surrogate

Phase Behavior and Viscosity in Biomass Burning Organic Aerosol and Climatic Impacts

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Resources

About

Heterogeneous oxidation of amorphous organic aerosol surrogates by O<sub>3</sub>, NO<sub>3</sub>, and OH at typical tropospheric temperatures

Heterogeneous oxidation of amorphous organic aerosol surrogates by O<sub>3</sub>, NO<sub>3</sub>, and OH at typical tropospheric temperatures