Isotope analysis of snowpack nitrate in coastal Antarctica; evidence of nitrate photolysis and preservation.

Photolysis of snowpack nitrate results in emission of the reactive nitrogen species NOx and HONO. These are important pre-cursors of HOx radicals and ozone, and thereby affect the oxidising capacity of the lower atmosphere above remote snow-covered areas. This is of particular importance in the polar regions as the usual OH radical formation pathway (ozone photolysis and reaction of O(1D) with H2O) is limited by the low water vapour concentration. Isotope analysis of atmospheric reactive nitrogen species and snow nitrate is proving to be a crucial tool for elucidating mechanisms of reactive nitrogen cycling in and above snow. The first snowpit profiles of nitrate stable isotopes (δ15N, δ18O) and concentration at Halley VI Research Station in coastal Antarctica will be presented. The observed isotope fractionation provides evidence of photochemical loss of nitrate and allows estimation of the photolytic isotope fractionation constant at the site. At this high accumulation site, the peak in nitrate concentration from the previous summer is preserved below the snow surface, unlike at low accumulation sites on the Antarctic Plateau. Combining measurements of nitrate concentration and its isotopic compositions preserved in snow helps disentangle the isotope signature of seasonal changes in atmospheric nitrate sources from post-depositional isotope fractionation occurring even at high snow accumulation sites.