An investigation of ClO photochemistry in the chemically perturbed Arctic vortex
J.M. Pierson, K.A. McKinney, D.W. Toohey, J.J. Margitan, U. Schmidt, A. Engel, P. A. Newman, J. Atmos. Chem., 32, 61-81, 1999.

A new lightweight in situ instrument designed to measure ClO was flown on a balloon launched into the arctic vortex at dawn on February 3, 1995 at Kiruna, Sweden during the Second European Stratospheric Arctic and Mid-latitude Experiment (SESAME), together with instruments to measure ozone and long-lived tracers. Observations  on ascent and descent at different solar zenith angles are compared to results from Lagrangian and box model calculations that assume the airmasses at similar potential temperatures had comparable photochemical histories. Between 20 and 22 km, in a region where ClO was significantly enhanced, a model constrained by currently recommended rate parameters significantly underestimates the abundances of ClO that were observed on ascent at higher solar zenith angles, whereas the agreement is much better if a smaller ClO-Cl2O2 equilibrium constant, one inferred from previous ER-2 aircraft observations of ClO in the Arctic during nighttime, is assumed. On ascent, ClO is additionally enhanced in a narrow region between 20 and 21 km. We believe the most plausible explanation for this feature is rapid photolysis of OClO produced by the slow bimolecular reaction ClO + ClO over the 48 hours prior to the observations when the airmass was warmed to 225 K by adiabatic compression while in polar darkness. These results suggest that under special circumstances, OClO can be produced by a reaction other than the one involving BrO, and, hence, OClO is not necessarily a universal proxy for BrO abundances in the perturbed polar vortex.