title: Constraining the chlorine monoxide (ClO)/chlorine peroxide (ClOOCl) equilibrium constant from Aura Microwave Limb Sounder measurements of nighttime ClO.
abstract: The primary ozone loss process in the cold polar lower stratosphere hinges on chlorine monoxide (ClO) and one of its dimers, chlorine peroxide (ClOOCl). Recently, analyses of atmospheric observations have suggested that the equilibrium constant, K(eq), governing the balance between ClOOCl formation and thermal decomposition in darkness is lower than that in the current evaluation of kinetics data. Measurements of ClO at night, when ClOOCl is unaffected by photolysis, provide a useful means of testing quantitative understanding of the ClO/ClOOCl relationship. Here we analyze nighttime ClO measurements from the National Aeronautics and Space Administration Aura Microwave Limb Sounder (MLS) to infer an expression for K(eq). Although the observed temperature dependence of the nighttime ClO is in line with the theoretical ClO/ClOOCl equilibrium relationship, none of the previously published expressions for K(eq) consistently produces ClO abundances that match the MLS observations well under all conditions. Employing a standard expression for K(eq), A x exp(B/T), we constrain the parameter A to currently recommended values and estimate B using a nonlinear weighted least squares analysis of nighttime MLS ClO data. ClO measurements at multiple pressure levels throughout the periods of peak chlorine activation in three Arctic and four Antarctic winters are used to estimate B. Our derived B leads to values of K(eq) that are approximately 1.4 times smaller at stratospherically relevant temperatures than currently recommended, consistent with earlier studies. Our results are in better agreement with the newly updated (2009) kinetics evaluation than with the previous (2006) recommendation.
authors.affiliation: Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA.
authors.forename: Michelle L
authors.initials: ML
authors.lastname: Santee
authors.forename: Stanley P
authors.initials: SP
authors.lastname: Sander
authors.forename: Nathaniel J
authors.initials: NJ
authors.lastname: Livesey
authors.forename: Lucien
authors.initials: L
authors.lastname: Froidevaux
mesh_terms: D001272:Atmosphere; D002713:Chlorine / Q000737:chemistry*; D004784:Environmental Monitoring / Q000379:methods*; D007700:Kinetics; D008872:Microwaves; D010087:Oxides / Q000737:chemistry*; D010545:Peroxides / Q000737:chemistry*; D012621:Seasons; D013696:Temperature
chemical_list: D010087:Oxides; D010545:Peroxides; D002713:Chlorine
references.citation: Science. 2007 Dec 21;318(5858):1878-9
references.pmid: 18096795
references.citation: J Phys Chem A. 2007 May 24;111(20):4322-32
references.pmid: 17474723
references.citation: J Phys Chem A. 2005 Aug 4;109(30):6730-4
references.pmid: 16834026
references.citation: Science. 2009 May 8;324(5928):781-4
references.pmid: 19423825
references.citation: J Phys Chem A. 2006 Mar 9;110(9):3280-8
references.pmid: 16509654