Nitric acid partitioning in cirrus clouds: a synopsis based on field, laboratory and model studies
Résumé
From a synopsis of field, laboratory and model studies at T>205 K as well as from the field experiments POLSTAR at T<205 K we derive a general picture of the partitioning of nitric acid (HNO3) in cirrus clouds and a new hypothesis on the uptake of HNO3 on ice particles:
A substantial part of nitric acid remains in the gas phase under cirrus cloud conditions. The HNO3 removed from the gas phase is distributed between interstitial aerosol and ice particles in dependence on the temperature and ice surface, respectively. In cold cirrus clouds with small ice surface areas (T <205 K) the partitioning is strongly in favour of interstitial ternary solution particles while in warmer cirrus clouds with large ice surface areas the uptake on ice dominates. Consequently, denitrification via sedimenting ice particles may occur only in the -more frequently occurring- warm cirrus clouds
The HNO3 coverage on ice is found to be different for ice particles and ice films. On ice films the coverage can increase with decreasing temperature from about 0.1 to 0.8 monolayer, while that on ice particles is found to decrease with temperature and PHNO3 from 0.1 to 0.001 monolayer. An HNO3 uptake behaviour following dissociative Langmuir isotherms where the coverage decreases for descending temperatures may explain the observations for ice particles
From a comparison of the HNO3 measurements with model calculations it is found that (i) the global model of Lawrence and Crutzen (1998) overestimates the HNO3 partitioning in favour of the ice particles (ii) the Langmuir surface chemistry model of Tabazadeh et al. (1999) overestimates HNO3 coverages for temperatures ?210 K More appropriate coverages are calculated when implementing in that model a temperature dependent function for the adsorption free energy (?Gads (T)), which is empirically derived from the coverage measurements.
A substantial part of nitric acid remains in the gas phase under cirrus cloud conditions. The HNO3 removed from the gas phase is distributed between interstitial aerosol and ice particles in dependence on the temperature and ice surface, respectively. In cold cirrus clouds with small ice surface areas (T <205 K) the partitioning is strongly in favour of interstitial ternary solution particles while in warmer cirrus clouds with large ice surface areas the uptake on ice dominates. Consequently, denitrification via sedimenting ice particles may occur only in the -more frequently occurring- warm cirrus clouds
The HNO3 coverage on ice is found to be different for ice particles and ice films. On ice films the coverage can increase with decreasing temperature from about 0.1 to 0.8 monolayer, while that on ice particles is found to decrease with temperature and PHNO3 from 0.1 to 0.001 monolayer. An HNO3 uptake behaviour following dissociative Langmuir isotherms where the coverage decreases for descending temperatures may explain the observations for ice particles
From a comparison of the HNO3 measurements with model calculations it is found that (i) the global model of Lawrence and Crutzen (1998) overestimates the HNO3 partitioning in favour of the ice particles (ii) the Langmuir surface chemistry model of Tabazadeh et al. (1999) overestimates HNO3 coverages for temperatures ?210 K More appropriate coverages are calculated when implementing in that model a temperature dependent function for the adsorption free energy (?Gads (T)), which is empirically derived from the coverage measurements.
Domaines
Océan, Atmosphère
Origine : Accord explicite pour ce dépôt