Interpretation of NO3− variability recorded in ice cores remains challenging as it can be lost from snow. Here, we present 60‐year records of NO3− and its isotopic composition (δ15N, δ18O, and Δ17O) in snow in central Antarctica, Dome A. In the upper ∼90 cm snowpack, variations in concentration and isotopic composition of NO3− are dominated by photolytic loss, and δ18O and Δ17O of NO3− are associated with the recycling of NOx to NO3− in the condensed phase driven by photolysis. In the deeper snowpack (∼1960–2000), we observe prolonged trends in concentration and isotopic composition of NO3−, which are best explained as enhanced snow NO3− photolysis due to long‐term decreasing total column ozone (TCO). That is, the prolonged period of trends in NO3− and its isotopes in extremely low snow accumulation sites such as Dome A relay information on variations in TCO and consequently surface solar ultraviolet radiation over time.
Snow nitrate is vulnerable to photolytic loss that causes isotopic alteration, and thus its isotopes can potentially track the extent of snow nitrate photolysis and its impacts in environments where loss is significant. Large increases in δ15N‐NO3− below the snow surface have been attributed to photolysis and this behavior is generally consistent amongst theoretical as well as lab and field studies. Oxygen isotope ratios are thought to be influenced by photolysis as well as secondary condensed‐phase chemistry, but the competing effects have yet to be reconciled. Here we use a model that simulates nitrate burial, photolytic fractionation, and re‐oxidation in snow to quantitatively assess these processes with the aim of developing a consistent framework for interpreting the photolytic effects of the complete nitrate isotopic composition (δ15N, δ18O, and Δ17O). This study reveals that isotopic effects of nitrate photolysis and aqueous‐phase re‐oxidation chemistry are important sources of uncertainties in modeling δ18O‐NO3−.
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