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RESEARCH ARTICLE

Consumption of reactive halogen species from sea-salt aerosol by secondary organic aerosol: slowing down the bromine explosion

Joelle Buxmann A B H , Sergej Bleicher A , Ulrich Platt B , Roland von Glasow C , Roberto Sommariva C G , Andreas Held D , Cornelius Zetzsch A E and Johannes Ofner F
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A Atmospheric Chemistry Research Laboratory, University of Bayreuth, Dr Hans-Frisch-Straße 1-3, D-95448 Bayreuth, Germany.

B Institute of Environmental Physics, University of Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany.

C Centre for Ocean and Atmospheric Sciences, School of Environmental Sciences, University of East Anglia, Norwich Research Park, Norfolk, NR4 7TJ, Norwich, UK.

D Atmospheric Chemistry, University of Bayreuth, Dr Hans-Frisch-Straße 1-3, D-95448 Bayreuth, Germany.

E Max Planck Institute for Chemistry, Hahn-Meitner Weg 1, D-55128 Mainz, Germany.

F Institute of Chemical Technologies and Analytics, TU Wien, Getreidemarkt 9, A-1060 Vienna, Austria.

G Present address: Department of Chemistry, University of Leicester, University Road, Leicester, LE1 7RH, UK.

H Corresponding author. Present address: Met Office, Exeter, Fitzroy Road, Devon, EX1 3PB, UK. Email: joelle.c.buxmann@metoffice.gov.uk

Environmental Chemistry 12(4) 476-488 https://doi.org/10.1071/EN14226
Submitted: 16 October 2014  Accepted: 8 May 2015   Published: 21 July 2015

Environmental context. Secondary organic aerosols together with sea-salt aerosols are a major contribution to global aerosols and influence the release of reactive halogens, which affect air quality and human health. In this study, the loss of reactive halogen species from simulated salt aerosols due to three different types of secondary organic aerosols was quantified in chamber experiments and investigated with the help of a numerical model. The loss rate can be included into chemistry models of the atmosphere and help to quantify the halogen budget in nature.

Abstract. The interaction between secondary organic aerosols (SOAs) and reactive bromine species (e.g. BrO, Br2, HOBr) coexisting in the environment is not well understood and not included in current chemistry models. The present study quantifies the quenching of bromine release from an artificial salt aerosol caused by SOAs from ozonolysis of three precursors (α-pinene, catechol or guaiacol) in a Teflon smog chamber and incorporates it into a chemical box model. The model simulations perform very well for a blank experiment without SOA precursor, capturing BrO formation, as detected by differential optical absorption spectrometry. A first-order BrO loss rate of 0.001 s–1 on the surface of SOA represents the overall effective Brx (total inorganic bromine) loss included in the model. Generally, the model agrees with the maximum BrO mixing ratio in time and magnitude, with some disagreements in the exact shape. Formation of reactive OClO was observed in the presence of organics but could not be reproduced by the model. According to current knowledge, most inorganic chlorine would be in the form of HCl in the presence of organics, as predicted by the model. In order to reproduce the net effects of the presence of SOA, the effective uptake coefficients of reactive bromine on the SOA surface are estimated to be 0.01, 0.01 and 0.004 for α-pinene, catechol and guaiacol respectively. The uptake coefficient can now be incorporated into box models and even global models, where sinks for bromine species are thought to be inadequately represented.

Additional keywords: atmospheric model, uptake coefficient.


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