Peroxyacetyl nitrate (PAN) concentrations in the Antarctic troposphere measured during the photochemical experiment at Neumayer (PEANʹ99)

Because investigations of PAN at higher southern latitudes are very scarce, we measured surface PAN concentrations for the first time in Antarctica. During the Photochemical Experiment at Neumayer (PEANʹ99) campaign mean surface PAN mixing ratios of 13±7 pptv and maximum values of 48 pptv were found. When these PAN mixing ratios were compared to the sum of NOx and inorganic nitrate they were found to be equal or higher. Low ambient air temperatures and low PAN concentrations caused a slow homogeneous PAN decomposition rate of approximately 5×10−2 pptv h−1. These slow decay rates were not sufficient to firmly establish the simultaneously observed NOx concentrations. In addition, low concentration ratios of [HNO3]/[NOx] imply that the photochemical production of NOx within the snow pack can influence surface NOx mixing ratios in Antarctica. Alternate measurements of PAN mixing ratios at two different heights above the snow surface were performed to derive fluxes between the lower troposphere and the underlying snow pack using calculated friction velocities. Most of the concentration differences were below the precision of the measurements. Therefore, only an upper limit for the PAN flux of ±1×1013 molecules m−2 s−1 without a predominant direction can be estimated. However, PAN fluxes below this limit can still influence both the transfer of nitrogen compounds between atmosphere and ice, and the PAN budget in higher southern latitudes.