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We report the first measurements of the oxygen isotope anomaly of atmospheric inorganic nitrate from the Arctic. Nitrate samples and complementary data were collected at Alert, Nunavut, Canada (82 30 0 N, 62 19 0 W) in spring 2004. Covering the polar sunrise period, characterized by the occurrence of severe boundary layer ozone depletion events (ODEs), our data show a significant correlation between the variations of atmospheric ozone (O3) mixing ratios and 1 17 O of nitrate (1 17 O(NO 3 )). This relationship can be expressed as: 1 17 O(NO 3 )/‰ = (0.15±0.03)◊O3/ (nmol mol 1 )+(29.7±0.7), with R 2 =0.70(n=12), for 1 17 O(NO 3 ) ranging between 29 and 35 ‰. We derive mass-balance equations from chemical reac- tions operating in the Arctic boundary layer, that describe the evolution of 1 17 O(NO 3 ) as a function of the concentrations of reactive species and their isotopic characteristics. Changes in the relative importance of O3, RO2 and BrO in the oxida- tion of NO during ODEs, and the large isotope anomalies of O3 and BrO, are the driving force for the variability in the measured 1 17 O(NO 3 ). BrONO2 hydrolysis is found to be a dominant source of nitrate in the Arctic boundary layer, in agreement with recent modeling studies.

Signature of Arctic surface ozone depletion events in the isotope anomaly (Δ&lt;sup&gt;17&lt;/sup&gt;O) of atmospheric nitrate

Signature of Arctic surface ozone depletion events in the isotope anomaly (Δ<sup>17</sup>O) of atmospheric nitrate