Modelling the physical multiphase interactions of HNO3 between snow and air on the Antarctic Plateau (Dome C) and coast (Halley)

• Published in: Atmospheric Chemistry and Physics
• Main Authors: Chan, Hoi Ga, Frey, Markus, King, Martin
• Format: Article in Journal/Newspaper
• Language: English
• Published: Copernicus Publications on behalf of the European Geosciences Union 2018
• Subjects: Antarctic; The Antarctic; Antarc*
• Online Access: http://nora.nerc.ac.uk/id/eprint/515290/; https://nora.nerc.ac.uk/id/eprint/515290/1/Chan.pdf; https://www.atmos-chem-phys.net/18/1507/2018/

Emissions of nitrogen oxide (NOx = NO + NO2) from the photolysis of nitrate (NO3−) in snow affect the oxidising capacity of the lower troposphere especially in remote regions of high latitudes with little pollution. Current air–snow exchange models are limited by poor understanding of processes and often require unphysical tuning parameters. Here, two multiphase models were developed from physically based parameterisations to describe the interaction of nitrate between the surface layer of the snowpack and the overlying atmosphere. The first model is similar to previous approaches and assumes that below a threshold temperature, To, the air–snow grain interface is pure ice and above To a disordered interface (DI) emerges covering the entire grain surface. The second model assumes that air–ice interactions dominate over all temperatures below melting of ice and that any liquid present above the eutectic temperature is concentrated in micropockets. The models are used to predict the nitrate in surface snow constrained by year-round observations of mixing ratios of nitric acid in air at a cold site on the Antarctic Plateau (Dome C; 75°06′ S, 123°33′ E; 3233 m a.s.l.) and at a relatively warm site on the Antarctic coast (Halley; 75°35′ S, 26°39′ E; 35 m a.s.l). The first model agrees reasonably well with observations at Dome C (Cv(RMSE) = 1.34) but performs poorly at Halley (Cv(RMSE) = 89.28) while the second model reproduces with good agreement observations at both sites (Cv(RMSE) = 0.84 at both sites). It is therefore suggested that in winter air–snow interactions of nitrate are determined by non-equilibrium surface adsorption and co-condensation on ice coupled with solid-state diffusion inside the grain, similar to Bock et al. (2016). In summer, however, the air–snow exchange of nitrate is mainly driven by solvation into liquid micropockets following Henry's law with contributions to total surface snow NO3− concentrations of 75 and 80 % at Dome C and Halley, respectively. It is also found that the liquid volume of ...