Arctic sea ice: an investigation into the origin of nitrate using δ15N, δ18O and Δ17O

Nitrogen (N) is essential to primary production and is made bioavailable through N2-fixation, and potentially, atmospheric deposition. While the Pacific delivers a significant supply of reactive N to the Arctic, it is unclear if atmospheric deposition helps fuel primary production in the N-deplete western Arctic Ocean. Sea ice and snow provide a unique opportunity to partition the end-member contributions of nitrate (NO3-) from the atmosphere to the ocean. Sea ice cores and snow samples were collected at six stations between 82 and 89°N as part of the U.S. Arctic GEOTRACES expedition in 2015. Sea ice samples had NO3- concentrations ranging from 0.2-1.0 µmol L-1 while snow samples were slightly higher ranging from 1.1-3.7 µmol L-1. The complete isotopic composition of NO3- (δ15N, δ18O, Δ17O) was measured using the denitrifier method on all snow samples and 32 core sub-samples. The Δ17O (Δ17O=δ17O-0.52*δ18O≠0) is a proven diagnostic tool for atmospheric NO3- compared to other NO3- sources because a nonzero Δ17O originates from the influence of ozone on the formation of NO3- in the atmosphere. Snow samples were characteristic of atmospheric NO3- with generally negative δ15N (-5.9-2‰) and highly enriched 17O and 18O (Δ17O=27.1-33.5‰; δ18O =70.8-87.8‰). In contrast, sea ice samples were more enriched in 15N (-0.3-15‰) and depleted in 17O and 18O (Δ17O=0-12.4‰; δ18O=23.3-67.5‰). The presence of a Δ17O>0‰ occurs at various depths, indicating that atmospheric NO3- is an important component of the NO3- found in sea ice. However, the lower Δ17O and δ18O values compared to snow suggest that a significant portion of the NO3- is either derived from seawater and/or issued from biological cycling of atmospheric/seawater reactive N in sea ice. Moreover, it appears that atmospheric NO3- is lost or consumed such that this biological processing of NO3- is most prominent. Recent trends in sea ice decline may result in future changes to the distribution of N in N-limited Arctic ecosystems.