Phosgene in the UTLS: seasonal and latitudinal variations from MIPAS observations

Abstract. The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) is a Fourier transform spectrometer that measured mid-infrared atmospheric limb emission spectra from July 2002 to April 2012 on board the polar-orbiting satellite ENVISAT. We have used MIPAS data to study the latitudinal variations of phosgene (COCl₂ or carbonyl chloride) and, for the first time, its seasonal variation in the upper troposphere/lower stratosphere region (UTLS). Retrievals of phosgene were made using the 830–860 cm⁻¹ region, corresponding to the ν₅ bands of COCl₂. Unfortunately, in that region, the ν₄ band of CFC-11, which is much stronger than COCl₂ ν₅, hides the phosgene emission. In order to evaluate seasonality and latitudinal distribution of phosgene we have analysed all the measurements made by MIPAS on days 18 and 20 of each month of 2008 with the optimized retrieval model (ORM) recently upgraded with the multi-target retrieval technique and with the optimal estimation functionality to apply external constraints to the state vector. Average seasonal profiles of phosgene show an evident latitudinal variability with the largest values observed in the tropical regions (maximum  ≈  35 parts per trillion by volume (pptv) at about 300 hPa). In the midlatitude and polar regions, the volume mixing ratio (VMR) values do not exceed 30 pptv and the vertical distributions are less peaked. Our analysis highlights that COCl₂ seasonal variability is fairly low, apart from the polar regions.