Deposition, recycling, and archival of nitrate stable isotopes between the air–snow interface: comparison between Dronning Maud Land and Dome C, Antarctica

V Holly L Winton,Anna E Jones,Xin Yang,Nicolas Caillon,Joel Savarino,Alison Ming,Lisa Hauge,Markus M Frey

doi:10.5194/acp-20-5861-2020

Abstract

Abstract. The nitrogen stable isotopic composition in nitrate (δ15N-NO3-) measured in ice cores from low-snow-accumulation regions in East Antarctica has the potential to provide constraints on past ultraviolet (UV) radiation and thereby total column ozone (TCO) due to the sensitivity of nitrate (NO3-) photolysis to UV radiation. However, understanding the transfer of reactive nitrogen at the air–snow interface in polar regions is paramount for the interpretation of ice core records of δ15N-NO3- and NO3- mass concentrations. As NO3- undergoes a number of post-depositional processes before it is archived in ice cores, site-specific observations of δ15N-NO3- and air–snow transfer modelling are necessary to understand and quantify the complex photochemical processes at play. As part of the Isotopic Constraints on Past Ozone Layer Thickness in Polar Ice (ISOL-ICE) project, we report new measurements of NO3- mass concentration and δ15N-NO3- in the atmosphere, skin layer (operationally defined as the top 5 mm of the snowpack), and snow pit depth profiles at Kohnen Station, Dronning Maud Land (DML), Antarctica. We compare the results to previous studies and new data, presented here, from Dome C on the East Antarctic Plateau. Additionally, we apply the conceptual 1D model of TRansfer of Atmospheric Nitrate Stable Isotopes To the Snow (TRANSITS) to assess the impact of NO3- recycling on δ15N-NO3- and NO3- mass concentrations archived in snow and firn. We find clear evidence of NO3- photolysis at DML and confirmation of previous theoretical, field, and laboratory studies that UV photolysis is driving NO3- recycling and redistribution at DML. Firstly, strong denitrification of the snowpack is observed through the δ15N-NO3- signature, which evolves from the enriched snowpack (−3 ‰ to 100 ‰), to the skin layer (−20 ‰ to 3 ‰), to the depleted atmosphere (−50 ‰ to −20 ‰), corresponding to mass loss of NO3- from the snowpack. Based on the TRANSITS model, we find that NO3- is recycled two times, on average, before it is archived in the snowpack below 15 cm and within 0.75 years (i.e. below the photic zone). Mean annual archived δ15N-NO3- and NO3- mass concentration values are 50 ‰ and 60 ng g−1, respectively, at the DML site. We report an e-folding depth (light attenuation) of 2–5 cm for the DML site, which is considerably lower than Dome C. A reduced photolytic loss of NO3- at DML results in less enrichment of δ15N-NO3- than at Dome C mainly due to the shallower e-folding depth but also due to the higher snow accumulation rate based on TRANSITS-modelled sensitivities. Even at a relatively low snow accumulation rate of 6 cm yr−1 (water equivalent; w.e.), the snow accumulation rate at DML is great enough to preserve the seasonal cycle of NO3- mass concentration and δ15N-NO3-, in contrast to Dome C where the depth profiles are smoothed due to longer exposure of surface snow layers to incoming UV radiation before burial. TRANSITS sensitivity analysis of δ15N-NO3- at DML highlights that the dominant factors controlling the archived δ15N-NO3- signature are the e-folding depth and snow accumulation rate, with a smaller role from changes in the snowfall timing and TCO. Mean TRANSITS model sensitivities of archived δ15N-NO3- at the DML site are 100 ‰ for an e-folding depth change of 8 cm, 110 ‰ for an annual snow accumulation rate change of 8.5 cm yr−1 w.e., 10 ‰ for a change in the dominant snow deposition season between winter and summer, and 10 ‰ for a TCO change of 100 DU (Dobson units). Here we set the framework for the interpretation of a 1000-year ice core record of δ15N-NO3- from DML. Ice core δ15N-NO3- records at DML will be less sensitive to changes in UV than at Dome C; however the higher snow accumulation rate and more accurate dating at DML allows for higher-resolution δ15N-NO3- records.

Highlights

Nitrate (NO−3 ) is a naturally occurring ion and plays a major role in the global nitrogen cycle
Based on the TRANSITS model, we find that NO−3 is recycled two times, on average, before it is archived in the snowpack below 15 cm and within 0.75 years
Primary sources of reactive nitrogen species to the Antarctic lower atmosphere and snowpack include the sedimentation of polar stratospheric clouds (PSCs) in late winter (Savarino et al, 2007), in addition to tropospheric transport of inorganic NO−3 from lightning, biomass burning and soil emissions (Lee et al, 2014), and, to a minor extent, advection of oceanic organic nitrate such as methyl nitrate (CH3NO3) and peroxyacyl nitrates (PAN) (Jacobi et al, 2000; Jones et al, 1999; Beyersdorf et al, 2010)

Summary

Introduction

Nitrate (NO−3 ) is a naturally occurring ion and plays a major role in the global nitrogen cycle. It is one of the most abundant ions in Antarctic snow and is commonly measured in ice cores Nitrate in polar ice provides constraints on past solar activity (Traversi et al, 2012), NO−3 sources, and the oxidative capacity of the atmosphere (Geng et al, 2017; Mulvaney and Wolff, 1993; Hastings et al, 2009, 2004; McCabe et al, 2007; Savarino et al, 2007; Morin et al, 2008). A local secondary source of reactive nitrogen (nitrous acid, HONO, and nitrogen oxides, NOx) originates from post-depositional processes driven by sunlight, leading to re-emission from the snowpack and subsequent deposition to surface snow (Jones et al, 2001; Honrath et al, 1999; Oncley et al, 2004; Frey et al, 2009; Savarino et al, 2007; Mulvaney et al, 1998)

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