Coupled evolution of BrO_x‐ClO_x‐HO_x‐NO_x chemistry during bromine‐catalyzed ozone depletion events in the arctic boundary layer

Extensive chemical characterization of ozone (O 3 ) depletion events in the Arctic boundary layer during the TOPSE aircraft mission in March–May 2000 enables analysis of the coupled chemical evolution of bromine (BrO x ), chlorine (ClO x ), hydrogen oxide (HO x ) and nitrogen oxide (NO x ) radicals during these events. We project the TOPSE observations onto an O 3 chemical coordinate to construct a chronology of radical chemistry during O 3 depletion events, and we compare this chronology to results from a photochemical model simulation. Comparison of observed trends in ethyne (oxidized by Br) and ethane (oxidized by Cl) indicates that ClO x chemistry is only active during the early stage of O 3 depletion (O 3 > 10 ppbv). We attribute this result to the suppression of BrCl regeneration as O 3 decreases. Formaldehyde and peroxy radical concentrations decline by factors of 4 and 2 respectively during O 3 depletion and we explain both trends on the basis of the reaction of CH 2 O with Br. Observed NO x concentrations decline abruptly in the early stages of O 3 depletion and recover as O 3 drops below 10 ppbv. We attribute the initial decline to BrNO 3 hydrolysis in aerosol, and the subsequent recovery to suppression of BrNO 3 formation as O 3 drops. Under halogen‐free conditions we find that HNO 4 heterogeneous chemistry could provide a major NO x sink not included in standard models. Halogen radical chemistry in the model can produce under realistic conditions an oscillatory system with a period of 3 days, which we believe is the fastest oscillation ever reported for a chemical system in the atmosphere.