Measurements of stratospheric chlorine monoxide (ClO) from groudbased FTIR observations

Abstract

Infrared absorption features due to ClO in the lower stratosphere have been identified from groundbased solar absorption spectra taken from Aberdeen, U.K. (57° N, 2° W) on 20 January 1995. A vertical column abundance of 3.42 (±0.47)×1015 molec cm-2 has been derived from 13 independent absorption features in the P and R branches of the (0–1) vibration-rotation band of 35ClO, spanning the spectral region 817–855 cm-1. The observed absorption features are consistent with very high levels of ClO (approximately 2.6 parts per billion by volume (ppbv)) in the altitude range 16–22 km. A comparison of this profile with a 3D chemical transport model profile indicates the observation was made inside the polar vortex and shows good qualitative agreement but the model underestimates the concentrations of ClO. Simultaneous measurements of other species were made including HCl, HF and ClONO2. These columns yield a value for HCl+ClONO2+ClO of 7.02±0.65×1015 molec cm-2. This is lower than the total inorganic chlorine (ClO y ) column of 10.7±1.6×1015 molec cm-2 estimated from mean measured (HCl+ClONO2)/HF ratios together with in-vortex HF measurements. The discrepancy is probably due to significant amounts of the ClO dimer (Cl2O2) in the lower part of the stratosphere. The measurements of highly elevated levels of ClO are used to estimate O3 loss rates at the 400, 475 and 550 K levels making assumptions about the probable distribution of ClO and Cl2O2. These are compared with loss rates derived from ozone sonde data.