Articles | Volume 15, issue 20
Atmos. Chem. Phys., 15, 12079–12113, 2015

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

Atmos. Chem. Phys., 15, 12079–12113, 2015

Research article 30 Oct 2015

Research article | 30 Oct 2015

Air–snow transfer of nitrate on the East Antarctic Plateau – Part 2: An isotopic model for the interpretation of deep ice-core records

J. Erbland1,2, J. Savarino1,2, S. Morin3, J. L. France4,a, M. M. Frey5, and M. D. King4 J. Erbland et al.
  • 1Université Grenoble Alpes, LGGE, 38000 Grenoble, France
  • 2CNRS, LGGE, 38000 Grenoble, France
  • 3Météo-France – CNRS, CNRM – GAME UMR 3589, CEN, Grenoble, France
  • 4Department of Earth Sciences, Royal Holloway University of London, Egham, Surrey, TW20 0EX, UK
  • 5British Antarctic Survey, Natural Environment Research Council, Cambridge, UK
  • anow at: School of Environmental Sciences, University of East Anglia, Norwich, NR4 7TJ, UK

Abstract. Unraveling the modern budget of reactive nitrogen on the Antarctic Plateau is critical for the interpretation of ice-core records of nitrate. This requires accounting for nitrate recycling processes occurring in near-surface snow and the overlying atmospheric boundary layer. Not only concentration measurements but also isotopic ratios of nitrogen and oxygen in nitrate provide constraints on the processes at play. However, due to the large number of intertwined chemical and physical phenomena involved, numerical modeling is required to test hypotheses in a quantitative manner. Here we introduce the model TRANSITS (TRansfer of Atmospheric Nitrate Stable Isotopes To the Snow), a novel conceptual, multi-layer and one-dimensional model representing the impact of processes operating on nitrate at the air–snow interface on the East Antarctic Plateau, in terms of concentrations (mass fraction) and nitrogen (δ15N) and oxygen isotopic composition (17O excess, Δ17O) in nitrate. At the air–snow interface at Dome C (DC; 75° 06' S, 123° 19' E), the model reproduces well the values of δ15N in atmospheric and surface snow (skin layer) nitrate as well as in the δ15N profile in DC snow, including the observed extraordinary high positive values (around +300 ‰) below 2 cm. The model also captures the observed variability in nitrate mass fraction in the snow. While oxygen data are qualitatively reproduced at the air–snow interface at DC and in East Antarctica, the simulated Δ17O values underestimate the observed Δ17O values by several per mill. This is explained by the simplifications made in the description of the atmospheric cycling and oxidation of NO2 as well as by our lack of understanding of the NOx chemistry at Dome C. The model reproduces well the sensitivity of δ15N, Δ17O and the apparent fractionation constants (15ϵapp, 17Eapp) to the snow accumulation rate. Building on this development, we propose a framework for the interpretation of nitrate records measured from ice cores. Measurement of nitrate mass fractions and δ15N in the nitrate archived in an ice core may be used to derive information about past variations in the total ozone column and/or the primary inputs of nitrate above Antarctica as well as in nitrate trapping efficiency (defined as the ratio between the archived nitrate flux and the primary nitrate input flux). The Δ17O of nitrate could then be corrected from the impact of cage recombination effects associated with the photolysis of nitrate in snow. Past changes in the relative contributions of the Δ17O in the primary inputs of nitrate and the Δ17O in the locally cycled NO2 and that inherited from the additional O atom in the oxidation of NO2 could then be determined. Therefore, information about the past variations in the local and long-range processes operating on reactive nitrogen species could be obtained from ice cores collected in low-accumulation regions such as the Antarctic Plateau.

Short summary
In this paper, we describe the development of a numerical model which aims at representing nitrate recycling at the air-snow interface on the East Antarctic Plateau. Stable isotopes are used as diagnostic and evaluation tools by comparing the model's results to recent field measurements of nitrate and key atmospheric species at Dome C, Antarctica. From sensitivity tests conducted with the model, we propose a framework for the interpretation of the nitrate isotope record in deep ice cores.
Final-revised paper