Chemistry of Multiphase Atmospheric Systems

Jaeschke, W.

doi:10.1007/978-3-642-70627-1

Cited by 55 publications

(2 citation statements)

References 224 publications

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“…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). The heterogeneous reaction kinetics are often expressed by the reactive uptake coefficient (γ), which represents the fraction of gas collisions with a substrate surface that yield uptake or reaction (Pöschl et al, 2007;Schwartz, 1986).…”

Section: Introductionmentioning

confidence: 99%

“…The effect of temperature on uptake kinetics via its impact on the condensed phase state has also been highlighted in a recent modeling study (Mu et al, 2018), which showed that low temperature conditions can substantially increase the lifetime of PAHs against O 3 and enhance their dispersion through both the planetary boundary layer and the free troposphere. Temperature also impacts the other processes involved in multiphase kinetics (Schwartz, 1986;Pöschl et al, 2007), including the collision flux of gas-phase species, the desorption rate and surface and bulk reaction rates, both typically expressed by an Arrhenius factor (Laidler et al, 1940;Pöschl et al, 2007;Baetzold and Somorjai, 1976). Clearly, the temperature dependency of the https://doi.org/10.5194/acp-2020-82 Preprint.…”

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: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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Abiotic Degradation in the Atmosphere

Klöpffer¹,

Wagner²

2007

Atmospheric Degradation of Organic Substances

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1)A sink is defi ned here as an irreversible chemical, photochemical or biochemical reaction which removes a molecule from the environment; a perfect sink leads to mineralization. Within this defi nition, the transfer to and the temporary fi xation in another compartment (e.g., soil, vegetation or water) without chemical modifi cation is not considered to be a sink [1].2 Photo-degradation in the Homogenous Gas Phase of the Troposphere Chapter 2: Abiotic Degradation in the Atmosphere 28 k OH (T) = (2.25 + 0.46 -0.39) × 10 -18 T 2 exp{(-910 ± 56)/T} cm 3 molecule -1 s -1 k OH (298 K) = 9.43 × 10 -15 cm 3 molecule -1 s -1More interesting for the average OH lifetime is k OH at the (weighted or effective) average temperature of the troposphere. This temperature has been estimated by Warneck [15] in an analysis of the tropospheric CH 4 + OH reaction as eff = 280 K. According to an earlier estimate, based on the lifetime of chlorinated hydrocarbons [34], this temperature may be as low as 260 K. Using the more recent estimate by Warneck, we obtain k OH (280 K) = 6.84 × 10 -15 cm 3 molecule -1 s -1The average tropospheric OH lifetimes of MCF is calculated to be τ OH = 9.3 a This value is higher than the average residence times calculated for MCF, which are based on long-term measurements of MCF concentrations and estimates of the amounts emitted yearly (see Section 5).MCF is photolysed at wavelengths around 200 nm [28] and can therefore act as a source of chlorine atoms in the stratosphere and contribute to ozone destruction. It has been phased out as a result of the Protocol of Montreal and its follow-up agreements.An up-to-date data collection of OH-reaction rate constants can be found in Chapter 3. Earlier critical data collections are mostly attributable to Roger Atkinson, whose group also measured many substances for the fi rst time

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Chemie in Wolken, Nebel und Niederschlag

Herrmann¹,

Jaeschke²,

Möller³

2007

Chemie in nserer Zeit

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Chemistry of Multiphase Atmospheric Systems

Cited by 55 publications

References 224 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

Abiotic Degradation in the Atmosphere

Chemie in Wolken, Nebel und Niederschlag

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Chemistry of Multiphase Atmospheric Systems

Cited by 55 publications

References 224 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

Abiotic Degradation in the Atmosphere

Chemie in Wolken, Nebel und Niederschlag

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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