1Centre National de Recherches Météorologiques-Groupe d'étude de l'Atmosphère Météorologique, Météo-France and CNRS, URA1357, Toulouse, France
2Laboratoire de Physique et Chimie de l'Environnement et de l'Espace, CNRS and University of Orléans, UMR7328, Orléans, France
Received: 29 Jun 2011 – Published in Atmos. Chem. Phys. Discuss.: 02 Nov 2011
Abstract. Bromoform is one of the most abundant halogenated Very Short-Lived Substances (VSLS) that possibly contributes, when degradated, to the inorganic halogen loading in the stratosphere. In this paper we present a detailed modelling study of the transport and the photochemical degradation of bromoform and its product gases (PGs) in a tropical convective cloud. The aim was to explore the transport and chemistry of bromoform under idealised conditions at the cloud scale. We used a 3-D cloud-resolving model coupled with a chemistry model including gaseous and aqueous chemistry. In particular, our model features explicit partitioning of the PGs between the gas phase and the aqueous phase based on newly calculated Henry's law coefficients using theoretical methods. We ran idealised simulations for up to 10 days that were initialised using a tropical radiosounding of atmospheric conditions and using outputs from a global chemistry-transport model for chemical species. Two simulations were run with stable atmospheric conditions with a bromoform initial mixing ratio of 40 pptv (part per trillion by volume) and 1.6 pptv up to 1 km altitude. The first simulation corresponds to high bromoform mixing ratios that are representative of real values found near strong localised sources (e.g. tropical coastal margins) and the second to the global tropical mean mixing ratio from observations. Both of these simulations show that the sum of bromoform and its PGs significantly decreases with time because of dry deposition, and that PGs are mainly in the form of HBr after 2 days of simulation. Two further simulations are conducted; these are similar to the first two simulations but include perturbations of temperature and moisture leading to the development of a convective cloud reaching the tropical tropopause layer (TTL). Results of these simulations show an efficient vertical transport of the bromoform from the boundary layer to the upper troposphere and the TTL. The bromoform mixing ratio in the TTL is up to 45% of the initial boundary layer mixing ratio. The most abundant organic PGs, which are not very soluble, are also uplifted efficiently in both simulations featuring the convective perturbation. The inorganic PGs are more abundant than the organic PGs, and their mixing ratios in the upper troposphere and in the TTL depend on the partitioning between inorganic soluble and insoluble species in the convective cloud. Important soluble species such as HBr and HOBr are efficiently scavenged by rain. This removal of Bry by rain is reduced by the release of Br2 (relatively insoluble) to the gas phase due to aqueous chemistry processes in the cloud droplets. The formation of Br2 in the aqueous phase and its subsequent release to the gas phase makes a non negligible contribution to the high altitude bromine budget in the case of the large bromoform (40 pptv) initial mixing ratios. In this specific, yet realistic case, this Br2 production process is important for the PG budget in the upper troposphere and in the TTL above convective systems. This process is favoured by acidic conditions in the cloud droplets, i.e. polluted conditions. In the case of low bromoform initial mixing ratios, which are more representative of the mean distribution in the tropics, this Br2 production process is shown to be less important. These conclusions could nevertheless be revisited if the knowledge of chlorine and bromine chemistry in the cloud droplets was improved in the future.
Revised: 25 Jun 2012 – Accepted: 26 Jun 2012 – Published: 16 Jul 2012
Marécal, V., Pirre, M., Krysztofiak, G., Hamer, P. D., and Josse, B.: What do we learn about bromoform transport and chemistry in deep convection from fine scale modelling?, Atmos. Chem. Phys., 12, 6073-6093, doi:10.5194/acp-12-6073-2012, 2012.