On the origin of the occasional spring nitrate peak in Greenland snow

Abstract. Ice core nitrate concentrations peak in the summer in both Greenland and Antarctica. Two nitrate concentration peaks in one annual layer have been observed some years in ice cores in Greenland from samples dating post-1900, with the additional nitrate peak occurring in the spring. The origin of the spring nitrate peak was hypothesized to be pollution transport from the mid-latitudes in the industrial era. We performed a case study on the origin of a spring nitrate peak in 2005 measured from a snowpit at Summit, Greenland, covering 3 years of snow accumulation. The effect of long-range transport of nitrate on this spring peak was excluded by using sulfate as a pollution tracer. The isotopic composition of nitrate (δ¹⁵N, δ¹⁸O and Δ¹⁷O) combined with photochemical calculations suggest that the occurrence of this spring peak is linked to a significantly weakened stratospheric ozone (O₃) layer. The weakened O₃ layer resulted in elevated UVB (ultraviolet-B) radiation on the snow surface, where the production of OH and NO_x from the photolysis of their precursors was enhanced. Elevated NO_x and OH concentrations resulted in enhanced nitrate production mainly through the NO₂ + OH formation pathway, as indicated by decreases in δ¹⁸O and Δ¹⁷O of nitrate associated with the spring peak. We further examined the nitrate concentration record from a shallow ice core covering the period from 1772 to 2006 and found 19 years with double nitrate peaks after the 1950s. Out of these 19 years, 14 of the secondary nitrate peaks were accompanied by sulfate peaks, suggesting long-range transport of nitrate as their source. In the other 5 years, low springtime O₃ column density was observed, suggesting enhanced local production of nitrate as their source. The results suggest that, in addition to direct transport of nitrate from polluted regions, enhanced local photochemistry can also lead to a spring nitrate peak. The enhanced local photochemistry is probably associated with the interannual variability of O₃ column density in the Arctic, which leads to elevated surface UV radiation in some years. In this scenario, enhanced photochemistry caused increased local nitrate production under the condition of elevated local NO_x abundance in the industrial era.