Seasonal variations in N and O isotopes of nitrate in snow at Summit, Greenland: Implications for the study of nitrate in snow and ice cores

Nitrogen and oxygen isotopes of NO3− have been measured in snow and firn from Summit, Greenland. The 15N/14N and 18O/16O ratios of NO3− in recently fallen snow are similar to those of surface snow. Diurnal variation is observed in 15N/14N of NO3−, and possibly 18O/16O, suggesting fractionating loss of NO3− from snow during the day, which is subsequently recovered at night. A larger seasonal variation is observed, with higher 15N/14N and lower 18O/16O of NO3− in summer than winter, which cannot be explained by postdepositional fractionation. The generally high 18O/16O of NO3− in Greenland snow (δ18O versus VSMOW = 65.2 to 79.6‰) indicates that oxygen atoms from ozone have been incorporated into NOx that was subsequently deposited as HNO3. The lower mean δ18O of NO3− in summer snow relative to winter (68.9‰ in summer 2000 and 70.5‰ in summer 2001 versus 77.5‰ in winter 2000–01) is a result of summertime HNO3 production via NO2 reaction with hydroxyl radical (OH), which dilutes the high δ18O imparted on NO2 from ozone. The higher mean 15N/14N of NO3− observed in snow from spring (δ15N versus air N2 = +5.9‰ in 2000 and −1.4‰ in 2001) and summer (+0.1‰ in 2000 and −0.8‰ in 2001) than fall (−9.2‰ in 2000) and winter (−10.0‰ in 2000–01) is more difficult to explain with seasonal photochemistry, given current knowledge. The seasonal 15N/14N change may reflect NOx sources, with a greater fall and wintertime contribution from fossil fuel emissions relative to other inputs of NOx (i.e., biogenic soil emissions, biomass burning, and lightning).