References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-11-8929-2011

The HNO3 forming branch of the HO2 + NO reaction: pre-industrial-to-present trends in atmospheric species and radiative forcings

Søvde

O. A.

¹ ³ Hoyle

C. R.

² ³ ⁴ Myhre

¹ Isaksen

I. S. A.

¹ ³

Center for International Climate and Environmental Research – Oslo (CICERO), Norway

Institute for Atmospheric and Climate Science, ETH Zurich, Zurich, Switzerland

Department of Geosciences, University of Oslo, Oslo, Norway

now at: Laboratory of Atmospheric Chemistry, Paul Scherrer Institut, Villigen, Switzerland

01 09 2011

11 17 8929 8943

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

This article is available from http://www.atmos-chem-phys.net/11/8929/2011/acp-11-8929-2011.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/8929/2011/acp-11-8929-2011.pdf

Recent laboratory measurements have shown the existence of a HNO3 forming branch of the HO2 + NO reaction. This reaction is the main source of tropospheric O3, through the subsequent photolysis of NO2, as well as being a major source of OH. The branching of the reaction to HNO3 reduces the formation of these species significantly, affecting O3 abundances, radiative forcing and the oxidation capacity of the troposphere. The Oslo CTM2, a three-dimensional chemistry transport model, is used to calculate atmospheric composition and trends with and without the new reaction branch. Results for the present day atmosphere, when both temperature and pressure effects on the branching ratio are accounted for, show an 11 % reduction in the calculated tropospheric burden of O3, with the main contribution from the tropics. An increase of the global, annual mean methane lifetime by 10.9 %, resulting from a 14.1 % reduction in the global, annual mean OH concentration is also found. Comparisons with measurements show that including the new branch improves the modelled O3 in the Oslo CTM2, but that it is not possible to conclude whether the NOy distribution improves. We model an approximately 11 % reduction in the tropical tropospheric O3 increase since pre-industrial times, and a 4 % reduction of the increase in total tropospheric burden. Also, an 8 % decrease in the trend of OH concentrations is calculated, when the new branch is accounted for. The radiative forcing due to changes in O3 over the industrial era was calculated as 0.33 W m−2, reducing to 0.26 W m−2 with the new reaction branch. These results are significant, and it is important that this reaction branching is confirmed by other laboratory groups.

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