References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-9-3075-2009

Radicals in the marine boundary layer during NEAQS 2004: a model study of day-time and night-time sources and sinks

Sommariva

¹ ² ⁴ Osthoff

H. D.

¹ ² ⁵ Brown

S. S.

¹ Bates

T. S.

³ Baynard

¹ ² ⁶ Coffman

³ de Gouw

J. A.

¹ ² Goldan

P. D.

² Kuster

W. C.

¹ Lerner

B. M.

¹ ² Stark

¹ ² Warneke

¹ ² Williams

E. J.

¹ ² Fehsenfeld

F. C.

² Ravishankara

A. R.

¹ Trainer

Earth System Research Laboratory, NOAA, Boulder, CO, USA

CIRES, University of Colorado, Boulder, CO, USA

Pacific Marine Environment Laboratory, NOAA, Seattle, WA, USA

now at: School of Environmental Sciences, University of East Anglia, Norwich, UK

now at: Department of Chemistry, University of Calgary, Calgary, Canada

now at: Lockheed Martin Coherent Technologies, Longmont, CO, USA

13 05 2009

9 9 3075 3093

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.

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The full text article is available as a PDF file from http://www.atmos-chem-phys.net/9/3075/2009/acp-9-3075-2009.pdf

This paper describes a modelling study of several HOx and NOx species (OH, HO2, organic peroxy radicals, NO3 and N2O5) in the marine boundary layer. A model based upon the Master Chemical Mechanism (MCM) was constrained to observations of chemical and physical parameters made onboard the NOAA ship R/V Brown as part of the New England Air Quality Study (NEAQS) in the summer of 2004. The model was used to calculate [OH] and to determine the composition of the peroxy radical pool. Modelled [NO3] and [N2O5] were compared to in-situ measurements by Cavity Ring-Down Spectroscopy. The comparison showed that the model generally overestimated the measurements by 30–50%, on average. The model results were analyzed with respect to several chemical and physical parameters, including uptake of NO3 and N2O5 on fog droplets and on aerosol, dry deposition of NO3 and N2O5, gas-phase hydrolysis of N2O5 and reactions of NO3 with NMHCs and peroxy radicals. The results suggest that fog, when present, is an important sink for N2O5 via rapid heterogeneous uptake. The comparison between the model and the measurements were consistent with values of the heterogeneous uptake coefficient of N2O5 (γN2O5)>1×10−2, independent of aerosol composition in this marine environment. The analysis of the different loss processes of the nitrate radical showed the important role of the organic peroxy radicals, which accounted for a significant fraction (median: 15%) of NO3 gas-phase removal, particularly in the presence of high concentrations of dimethyl sulphide (DMS).

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