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Volume 18, issue 10
Atmos. Chem. Phys., 18, 7109–7129, 2018
https://doi.org/10.5194/acp-18-7109-2018
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.
Atmos. Chem. Phys., 18, 7109–7129, 2018
https://doi.org/10.5194/acp-18-7109-2018
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 24 May 2018

Research article | 24 May 2018

Global modelling of the total OH reactivity: investigations on the “missing” OH sink and its atmospheric implications

Valerio Ferracci1,a, Ines Heimann1, N. Luke Abraham1,2, John A. Pyle1,2, and Alexander T. Archibald1,2 Valerio Ferracci et al.
  • 1Centre for Atmospheric Science, Department of Chemistry, University of Cambridge, Lensfield Road, CB2 1EW, UK
  • 2National Centre for Atmospheric Science, University of Cambridge, Cambridge, UK
  • anow at: Centre for Environmental and Agricultural Informatics, Cranfield University, College Road, MK43 0AL, UK

Abstract. The hydroxyl radical (OH) plays a crucial role in the chemistry of the atmosphere as it initiates the removal of most trace gases. A number of field campaigns have observed the presence of a missing OH sink in a variety of regions across the planet. A comparison of direct measurements of the OH loss frequency, also known as total OH reactivity (kOH), with the sum of individual known OH sinks (obtained via the simultaneous detection of species such as volatile organic compounds and nitrogen oxides) indicates that, in some cases, up to 80 % of kOH is unaccounted for. In this work, the UM-UKCA chemistry-climate model was used to investigate the wider implications of the missing reactivity on the oxidising capacity of the atmosphere. Simulations of the present-day atmosphere were performed and the model was evaluated against an array of field measurements to verify that the known OH sinks were reproduced well, with a resulting good agreement found for most species. Following this, an additional sink was introduced to simulate the missing OH reactivity as an emission of a hypothetical molecule, X, which undergoes rapid reaction with OH. The magnitude and spatial distribution of this sink were underpinned by observations of the missing reactivity. Model runs showed that the missing reactivity accounted for on average 6 % of the total OH loss flux at the surface and up to 50 % in regions where emissions of the additional sink were high. The lifetime of the hydroxyl radical was reduced by 3 % in the boundary layer, whilst tropospheric methane lifetime increased by 2 % when the additional OH sink was included. As no OH recycling was introduced following the initial oxidation of X, these results can be interpreted as an upper limit of the effects of the missing reactivity on the oxidising capacity of the troposphere. The UM-UKCA simulations also allowed us to establish the atmospheric implications of the newly characterised reactions of peroxy radicals (RO2) with OH. Whilst the effects of this chemistry on kOH were minor, the reaction of the simplest peroxy radical, CH3O2, with OH was found to be a major sink for CH3O2 and source of HO2 over remote regions at the surface and in the free troposphere. Inclusion of this reaction in the model increased tropospheric methane lifetime by up to 3 %, depending on its product branching. Simulations based on the latest kinetic and product information showed that this reaction cannot reconcile models with observations of atmospheric methanol, in contrast to recent suggestions.

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Short summary
Hydroxyl radicals (OH) control the removal of species emitted in the atmosphere. Field campaigns reported a "missing" OH sink, not included in current atmospheric models. In this work a global model was used to establish the impact of additional OH sinks, based on both observations of the missing sink and newly discovered reactions of OH. Results show modest increases in global atmospheric lifetimes but pronounced regional effects on the abundance of some key species.
Hydroxyl radicals (OH) control the removal of species emitted in the atmosphere. Field campaigns...
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