Open AccessCoupled evolution of BrO x ‐ClO x ‐HO x ‐NO x chemistry during bromine‐catalyzed ozone depletion events in the arctic boundary layer
Author(s) -
Evans M. J.,
Jacob D. J.,
Atlas E.,
Cantrell C. A.,
Eisele F.,
Flocke F.,
Fried A.,
Mauldin R. L.,
Ridley B. A.,
Wert B.,
Talbot R.,
Blake D.,
Heikes B.,
Snow J.,
Walega J.,
Weinheimer A. J.,
Dibb J.
Publication year - 2003
Publication title -
journal of geophysical research: atmospheres
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.67
H-Index - 298
eISSN - 2156-2202
pISSN - 0148-0227
DOI - 10.1029/2002jd002732
Subject(s) - bromine , halogen , ozone depletion , chemistry , ozone , radical , atmospheric chemistry , chlorine , oxide , catalysis , chemical reaction , organic chemistry , alkyl
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.