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Several zero-dimensional box-models with different levels of chemical complexity, based on the Master Chemical Mechanism (MCM), have been used to study the chemistry of OH and HO 2 in a coastal environment in the Northern Hemisphere. The models were constrained to and compared with measurements made during the NAMBLEX campaign (Mace Head, Ireland) in summer 2002. The base models, which were constrained to measured CO, CH 4 and NMHCs, were able to reproduce [OH] within 25%, but overestimated [HO 2 ] by about a factor of 2. Agreement was improved when the models were constrained to oxygenated compounds (acetaldehyde, methanol and acetone), highlighting their importance for the radical budget. When the models were constrained to measured halogen monoxides (IO, BrO) and used a more detailed, measurements-based, treatment to describe the heterogeneous uptake, modelled [OH] increased by up to 15% and [HO 2 ] decreased by up to 30%. The actual impact of halogen monoxides on the modelled concentrations of HO x was dependant on the uptake coefficients used for HOI, HOBr and HO 2 . Better agreement, within the combined uncertainties of the measurements and of the model, was achieved when using high uptake coefficients for HO 2 and HOI (γ HO 2 =1, γ HOI =0.6). A rate of production and destruction analysis of the models allowed a detailed study of OH and HO 2 chemistry under the conditions encountered during NAMBLEX, showing the importance of oxygenates and of XO (where X=I, Br) as co-reactants for OH and HO 2 and of HOX photolysis as a source for OH.

OH and HO&lt;sub&gt;2&lt;/sub&gt; chemistry during NAMBLEX: roles of oxygenates, halogen oxides and heterogeneous uptake

OH and HO<sub>2</sub> chemistry during NAMBLEX: roles of oxygenates, halogen oxides and heterogeneous uptake