Modelled and Measured Abundances of Free Radicals in the Marine Boundary Layer During NEAQS 2004 and TEXAQS 2006

Chemistry of free radicals in the marine boundary layer was investigated during two cruises of the NOAA Research Vessel Ronald H. Brown as parts of the NEAQS-ITCT 2004 and TexAQS-GoMACCS 2006 campaigns. The nitrate radical (NO{_3}) and dinitrogen pentoxide (N{_2}O{_5}) were measured during the NEAQS campaign by Cavity Ring-Down Spectroscopy (CaRDS). NO{_3} abundances measured under the conditions encountered during the cruise were investigated using a zero-dimensional model based upon the Master Chemical Mechanism (MCMv3.1, http://mcm.leeds.ac.uk). The model was constrained to measurements of chemical and physical parameters taken during the campaign. The high level of chemical detail in the MCM allowed us to calculate abundances of the alkyl peroxy radicals that were to be expected and to study the interactions during the night between these alkyl peroxy radicals (RO{_2}) and NO{_3}. In particular, the importance of the reaction between RO{_2} and NO{_3} as a sink for NO{_3} under different conditions was assessed. CaRDS NO{_3} measurements during TexAQS campaign were made in conjunction with measurements of total peroxy radicals (HO{_2}+RO{_2}) by a chemical amplification technique (PERCA), allowing for experimental verification of the relationships between these radicals at night. The preliminary measurements taken during TeXAQS 2006 will be presented and they will be used to investigate the night-time chemistry of the peroxy radicals, and especially the interactions between NO{_3} and peroxy radical in a polluted nighttime environment.