Factors influencing nitrogen isotopes of snow nitrate: implications for interpretations of ice core nitrate records
Tuesday, 16 December 2014: 10:20 AM
The records of nitrate concentration and its isotopic composition (δ15N, δ18O and Δ17O) in ice cores are sought to reconstruct past levels of atmospheric NOx, the natural variability in NOx sources, and variations in tropospheric oxidants. However, these practices have been hampered by post-depositional processing of snow nitrate, which alters snow nitrate concentrations as well as its isotopic composition. Snow accumulation rates influence the degree of post-depositional processing. At sites with high snow accumulation rates, such as Summit, Greenland, the degree of post-depositional processing is thought to be minimal. Thus, variations in δ15N(NO3-) in Summit ice cores have been linked to NOx source changes, assuming the conservation of nitrogen isotope signatures during the conversion of NOx to nitrate. However, the marked decrease in δ15N(NO3-) from ~1850 to 1970 observed in Summit ice cores is difficult to explain by the addition of anthropogenic NOx to the natural background, as higher atmospheric δ15N(NO3-) values are frequently observed in polluted regions compared to pristine regions. Alternatively, we hypothesized that this decrease can be explained by changes in atmospheric acidity. Atmospheric acidity influences the partitioning of nitrate in gas- and aerosol-phases, inducing isotopic effects. Increased atmospheric acidity beginning ~ 1850 arising from anthropogenic SO2 emissions leads to elevated gas-phase HNO3 which is depleted in δ15N relative to aerosol nitrate. The preferential transport of HNO3 to the Arctic then leads to a decrease in ice core δ15N(NO3-). This hypothesis is supported by the significant correlation between δ15N(NO3-) and acidity records, and is supported by a model simulation. The result of this study indicates the importance of atmospheric processes to ice core δ15N(NO3-), and suggests that the link between ice core δ15N(NO3-) and NOx sources could be problematic even at high snow accumulation sites. In addition, our δ15N(NO3-) measurements in Summit ice cores expanding to the glacial-interglacial timescale indicate clear evidence of the effects of post-depositional processing, making it even more difficult to link ice core δ15N(NO3-) variations to NOx source changes.