The diurnal variability of atmospheric nitrogen oxides (NO and NO 2) above the Antarctic Plateau driven by atmospheric stability and snow emissions
Atmospheric nitrogen oxides (NO and NO 2) were observed at Dome C, East Antarctica (75.1° S, 123.3° E, 3233 m), for a total of 50 days, from 10 December 2009 to 28 January 2010. Average (±1σ) mixing ratios at 1.0 m of NO and NO 2, the latter measured for the first time on the East Antarctic Plateau, were 111 (±89) and 98 (±89) pptv, respectively. Atmospheric mixing ratios are on average comparable to those observed previously at South Pole, but in contrast show strong diurnal variability: a minimum around local noon and a maximum in the early evening coincide with the development and collapse of a convective boundary layer. The asymmetric diurnal cycle of NO x concentrations and likely any other chemical tracer with a photolytic surface source is driven by the turbulent diffusivity and height of the atmospheric boundary layer, with the former controlling the magnitude of the vertical flux and the latter the size of the volume into which snow emissions are transported. In particular, the average (±1σ) NO x emission flux from 22 December 2009 to 28 January 2010, estimated from atmospheric concentration gradients, was 8.2 (±7.4) × 10 12 molecule m −2 s −1 belongs to the largest values measured so far in the polar regions and explains the 3-fold increase in mixing ratios in the early evening when the boundary layer becomes very shallow. Dome C is likely not representative for the entire East Antarctic Plateau but illustrates the need of an accurate description of the boundary layer above snow in atmospheric chemistry models. A simple nitrate photolysis model matches the observed median diurnal NO x flux during the day but has significant low bias during the night. The difference is significant taking into account the total random error in flux observations and model uncertainties due to the variability of NO 3− concentrations in snow and potential contributions from NO 2− photolysis. This highlights uncertainties in the parameterization of the photolytic NO x source in natural snowpacks, such as the poorly constrained quantum yield of nitrate photolysis. A steady-state analysis of the NO 2 : NO ratios indicates that peroxy (HO 2 + RO 2) or other radical concentrations in the boundary layer of Dome C are either higher than measured elsewhere in the polar regions or other processes leading to enhanced NO 2 have to be invoked. These results confirm the existence of a strongly oxidising canopy enveloping the East Antarctic Plateau in summer.