Evaluated kinetic and photochemical data for atmospheric chemistry:  Volume VI – heterogeneous reactions with liquid substrates

Ammann, Markus; Cox, R. A.; Crowley, John N.; Jenkin, Michael E.; Mellouki, Abdelwahid; Rossi, Michel J.; Troe, J.; Wallington, Timothy J.

doi:10.5194/acp-13-8045-2013

Cited by 182 publications

(273 citation statements)

References 106 publications

(204 reference statements)

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“…The uncertainty around the transition into zero-order uptake in this regime of uptake and the corresponding small overestimation of g and thus G s does not change the assessment of the lower limit. 34,38 This gives a value of around 7 Â 10 À5 s À1 as the lower limit for k I SLR . We also estimated the O 3 loss due to the surface reaction by subtracting the integral of the O 3 loss due to bulk processes from the integral of the total loss for the time period of up to 8 min.…”

Section: Steady-state Evaluationmentioning

confidence: 99%

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Shikimic acid ozonolysis kinetics of the transition from liquid aqueous solution to highly viscous glass

Steimer

Berkemeier

Gilgen

et al. 2015

Phys. Chem. Chem. Phys.

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Ageing of particulate organic matter affects the composition and properties of atmospheric aerosol particles. Driven by temperature and humidity, the organic fraction can vary its physical state between liquid and amorphous solid, or rarely even crystalline. These transitions can influence the reaction kinetics due to limitations of mass transport in such (semi-) solid states, which in turn may influence the chemical ageing of particles containing such compounds. We have used coated wall flow tube experiments to investigate the reaction kinetics of the ozonolysis of shikimic acid, which serves as a proxy for oxygenated, water-soluble organic matter and can form a glass at room temperature. Particular attention was paid to how the presence of water influences the reaction, since it acts a plasticiser and thereby induces changes in the physical state. We analysed the results by means of a traditional resistor model, which assumes steady-state conditions. The ozonolysis rate of shikimic acid is strongly increased in the presence of water, a fact we attribute to the increased transport of O-3 and shikimic acid through the condensed phase at lower viscosities. The analysis using the resistor model suggests that the system undergoes both surface and bulk reaction. The second-order rate coefficient of the bulk reaction is 3.7 (+1.5/-3.2) x 10(3) L mol(-1) s(-1). At low humidity and long timescales, the resistor model fails to describe the measurements appropriately. The persistent O-3 uptake at very low humidity suggests contribution of a self-reaction of O-3 on the surface

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Section: Steady-state Evaluationmentioning

confidence: 99%

“…Given the recommended bulk accommodation coefficient for O 3 on water (410 À3 ) 34 and assuming that surface accommodation is not limiting bulk accommodation, it is unlikely that surface accommodation is the rate limiting step. Eqn (2) then simplifies to…”

Section: Steady-state Evaluationmentioning

confidence: 99%

Shikimic acid ozonolysis kinetics of the transition from liquid aqueous solution to highly viscous glass

Steimer

Berkemeier

Gilgen

et al. 2015

Phys. Chem. Chem. Phys.

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“…The heterogeneous chemistry of sulfate aerosols in the stratosphere is fairly well understood (Ammann et al, 2013) -for example the conversion of NO x to nitric acid in the aerosol via N 2 O 5 adsorption and reaction, and also the activation of chlorine via the reaction of ClONO 2 with HCl to form Cl 2 and nitric acid within cold aerosols. However, the heterogeneous reactivity of mineral particles, in particular TiO 2 , is not as well understood.…”

Section: Introductionmentioning

confidence: 99%

Heterogeneous reaction of HO2 with airborne TiO2 particles and its implication for climate change mitigation strategies

Moon¹,

Taverna²,

Anduix‐Canto³

et al. 2018

Atmos. Chem. Phys.

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Abstract. One geoengineering mitigation strategy for global temperature rises resulting from the increased concentrations of greenhouse gases is to inject particles into the stratosphere to scatter solar radiation back to space, with TiO 2 particles emerging as a possible candidate. Uptake coefficients of HO 2 , γ (HO 2 ), onto sub-micrometre TiO 2 particles were measured at room temperature and different relative humidities (RHs) using an atmospheric pressure aerosol flow tube coupled to a sensitive HO 2 detector. Values of γ (HO 2 ) increased from 0.021 ± 0.001 to 0.036 ± 0.007 as the RH was increased from 11 to 66 %, and the increase in γ (HO 2 ) correlated with the number of monolayers of water surrounding the TiO 2 particles. The impact of the uptake of HO 2 onto TiO 2 particles on stratospheric concentrations of HO 2 and O 3 was simulated using the TOMCAT three-dimensional chemical transport model. The model showed that, when injecting the amount of TiO 2 required to achieve the same cooling effect as the Mt Pinatubo eruption, heterogeneous reactions between HO 2 and TiO 2 would have a negligible effect on stratospheric concentrations of HO 2 and O 3 .

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“…ClNO 2 ) resulting from the heterogeneous reactions of N 2 O 5 with chloride containing particles (Osthoff et al, 2008;Thornton et al, 2010;Phillips et al, 2012;Ammann et al, 2013;Phillips et al, 2016).…”

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confidence: 99%

Direct measurement of NO3 reactivity in a boreal forest

Liebmann

Karu

Sobanski

et al. 2017

Preprint

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Abstract. We present the first direct measurements of NO 3 reactivity (or inverse lifetime, s -1 ) in the Finnish boreal forest.The data were obtained during the IBAIRN campaign (Influence of Biosphere-Atmosphere Interactions on the Reactive 15 Nitrogen budget) which took place in Hyytiälä, Finland during the summer / autumn transition in September 2016. The NO 3 reactivity was generally very high with a maximum value of 0.94 s -1 and displayed a strong diel variation with a campaignaveraged nighttime mean value of 0.11 s -1 compared to a daytime value of 0.04 s -1 . The highest nighttime NO 3 -reactivity was accompanied by major depletion of canopy level ozone and was associated with strong temperature inversions and high levels of monoterpenes. The daytime reactivity was sufficiently large that reactions of NO 3 with organic trace gases could 20 compete with photolysis and reaction with NO. There was no significant reduction in the measured NO 3 reactivity between the beginning and end of the campaign indicating that any seasonal reduction in canopy emissions of reactive biogenic trace gases was offset by emissions from the forest floor. Observations of biogenic hydrocarbons (BVOC) suggested a dominant role for monoterpenes in determining the NO 3 reactivity. Reactivity not accounted for by in-situ measurement of NO and BVOCs was variable across the diel cycle with, on average, ≈ 30% "missing" during nighttime and ≈ 60% missing during 25 the day. Measurement of the NO 3 reactivity at various heights (8.5 to 25 m) both above and below the canopy, revealed a strong nighttime, vertical gradient with maximum values closest to the ground. The gradient disappeared during daytime due to efficient vertical mixing.

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Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VI – heterogeneous reactions with liquid substrates

Cited by 182 publications

References 106 publications

Shikimic acid ozonolysis kinetics of the transition from liquid aqueous solution to highly viscous glass

Shikimic acid ozonolysis kinetics of the transition from liquid aqueous solution to highly viscous glass

Heterogeneous reaction of HO<sub>2</sub> with airborne TiO<sub>2</sub> particles and its implication for climate change mitigation strategies

Direct measurement of NO<sub>3</sub> reactivity in a boreal forest

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Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VI – heterogeneous reactions with liquid substrates

Cited by 182 publications

References 106 publications

Shikimic acid ozonolysis kinetics of the transition from liquid aqueous solution to highly viscous glass

Shikimic acid ozonolysis kinetics of the transition from liquid aqueous solution to highly viscous glass

Heterogeneous reaction of HO&lt;sub&gt;2&lt;/sub&gt; with airborne TiO&lt;sub&gt;2&lt;/sub&gt; particles and its implication for climate change mitigation strategies

Direct measurement of NO&lt;sub&gt;3&lt;/sub&gt; reactivity in a boreal forest

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Product

Resources

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Heterogeneous reaction of HO<sub>2</sub> with airborne TiO<sub>2</sub> particles and its implication for climate change mitigation strategies

Direct measurement of NO<sub>3</sub> reactivity in a boreal forest