Articles | Volume 15, issue 19
Atmos. Chem. Phys., 15, 11243–11256, 2015

Special issue: Oxidant Production over Antarctic Land and its Export...

Atmos. Chem. Phys., 15, 11243–11256, 2015

Research article 09 Oct 2015

Research article | 09 Oct 2015

Isotopic effects of nitrate photochemistry in snow: a field study at Dome C, Antarctica

T. A. Berhanu1,2,a, J. Savarino1,2, J. Erbland1,2, W. C. Vicars1,2,b, S. Preunkert1,2, J. F. Martins3, and M. S. Johnson4 T. A. Berhanu et al.
  • 1Universite Grenoble Alpes, LGGE, 38041 Grenoble, France
  • 2CNRS, LGGE, 38000 Grenoble, France
  • 3LTHE, UMR 5564, UJF-Grenoble 1/CNRS-INSU/G-INP, 38041 Grenoble, France
  • 4Copenhagen Center for Atmospheric Research, Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen Ø, Denmark
  • acurrently at: Physics Institute, Climate and Environmental Physics, University of Bern, 3012 Bern, Switzerland
  • bcurrently at: Technical Services Program, Air Pollution Control Division, Colorado Department of Public Health and Environment, Denver, CO, USA

Abstract. Stable isotope ratios of nitrate preserved in deep ice cores are expected to provide unique and valuable information regarding paleoatmospheric processes. However, due to the post-depositional loss of nitrate in snow, this information may be erased or significantly modified by physical or photochemical processes before preservation in ice. We investigated the role of solar UV photolysis in the post-depositional modification of nitrate mass and stable isotope ratios at Dome C, Antarctica, during the austral summer of 2011/2012. Two 30 cm snow pits were filled with homogenized drifted snow from the vicinity of the base. One of these pits was covered with a plexiglass plate that transmits solar UV radiation, while the other was covered with a different plexiglass plate having a low UV transmittance. Samples were then collected from each pit at a 2–5 cm depth resolution and a 10-day frequency. At the end of the season, a comparable nitrate mass loss was observed in both pits for the top-level samples (0–7 cm) attributed to mixing with the surrounding snow. After excluding samples impacted by the mixing process, we derived an average apparent nitrogen isotopic fractionation (15ϵapp) of −67.8 ± 12 ‰ for the snow nitrate exposed to solar UV using the nitrate stable isotope ratios and concentration measurements. For the control samples in which solar UV was blocked, an apparent average 15ϵapp value of −12.0 ± 1.7 ‰ was derived. This difference strongly suggests that solar UV photolysis plays a dominant role in driving the isotopic fractionation of nitrate in snow. We have estimated a purely photolytic nitrogen isotopic fractionation (15ϵphoto) of −55.8 ± 12.0 ‰ from the difference in the derived apparent isotopic fractionations of the two experimental fields, as both pits were exposed to similar physical processes except exposure to solar UV. This value is in close agreement with the 15ϵphoto value of −47.9 ± 6.8 ‰ derived in a laboratory experiment simulated for Dome C conditions (Berhanu et al., 2014). We have also observed an insensitivity of 15ϵ with depth in the snowpack under the given experimental setup. This is due to the uniform attenuation of incoming solar UV by snow, as 15ϵ is strongly dependent on the spectral distribution of the incoming light flux. Together with earlier work, the results presented here represent a strong body of evidence that solar UV photolysis is the most relevant post-depositional process modifying the stable isotope ratios of snow nitrate at low-accumulation sites, where many deep ice cores are drilled. Nevertheless, modeling the loss of nitrate in snow is still required before a robust interpretation of ice core records can be provided.

Short summary
In this field study at Dome C, Antarctica, we investigated the effect of solar UV photolysis on the stable isotopes of nitrate in snow via comparison of two identical snow pits while exposing only one to solar UV. From the difference between the average isotopic fractionations calculated for each pit, we determined a purely photolytic nitrogen isotopic fractionation of -55.8‰, in good agreement with what has been recently determined in a laboratory study.
Final-revised paper