Atmospheric nitric oxide and ozone at the WAIS Divide deep coring site: a discussion of local sources and transport in West Antarctica

The first measurements of atmospheric nitric oxide (NO) along with observations of ozone (O-3), hydroperoxides (H2O2 and MHP) and snow nitrate (NO3-) on the West Antarctic Ice Sheet (WAIS) were carried out at the WAIS Divide deep ice-coring site between 10 December 2008 and 11 January 2009. Average +/- 1 sigma mixing ratios of NO were 19 +/- 31 pptv and confirmed prior model estimates for the summer boundary layer above WAIS. Mean +/- 1 sigma mixing ratios of O-3 of 14 +/- 4 ppbv were in the range of previous measurements from overland traverses across WAIS during summer, while average +/- 1 sigma concentrations of H2O2 and MHP revealed higher levels with mixing ratios of 743 +/- 362 and 519 +/- 238 pptv, respectively. An upper limit for daily average NO2 and NO emission fluxes from snow of 8.6x10(8) and 33.9x10(8) molecule cm(-2) s(-1), respectively, were estimated based on photolysis of measured NO3- and nitrite (NO2-) in the surface snowpack. The resulting high NOx emission flux may explain the little preservation of NO3- in snow (similar to 30 %) when compared to Summit, Greenland (75-93%). Assuming rapid and complete mixing into the overlying atmosphere, and steady state of NOx, these snow emissions are equivalent to an average (range) production of atmospheric NOx of 30 (21-566) pptv h(-1) for a typical atmospheric boundary-layer depth of 250 (354-13) m. These upper bounds indicate that local emissions from the snowpack are a significant source of short-lived nitrogen oxides above the inner WAIS. The net O-3 production of 0.8 ppbv day(-1) triggered with NO higher than 2 pptv is too small to explain the observed O-3 variability. Thus, the origins of the air masses reaching WAIS Divide during this campaign were investigated with a 4-day back-trajectory analysis every 4 h. The resulting 168 back trajectories revealed that in 75% of all runs air originated from the Antarctic coastal slopes (58%) and the inner WAIS (17%). For these air sources O-3 levels were on average 13 +/- 3 ppbv. The remaining 25% are katabatic outflows from the East Antarctic Plateau above 2500 m. When near-surface air from the East Antarctic Plateau reaches WAIS Divide through a rapid transport of less than 3 days, O-3 levels are on average 19 +/- 4 ppbv with maximum mixing ratios of 30 ppbv. Episodes of elevated ozone at WAIS Divide are therefore linked to air mass export off the East Antarctic Plateau, demonstrating that outflows from the highly oxidizing summer atmospheric boundary layer in the interior of the continent can episodically raise the mixing ratios of long-lived atmospheric chemical species such as O-3 and enhance the oxidative capacity of the atmosphere above WAIS.