Investigating the sensitivity of surface-level nitrate seasonality in Antarctica to primary sources using a global model

Determining the sources of total nitrate (TNIT ≡ NO3− + HNO3) reaching Antarctica is a long-standing challenge. Here we analyze the monthly sensitivity of surface-level TNIT in Antarctica to primary sources using a global 3-D chemical transport model, GEOS-Chem, and its adjoint. Modeled seasonal variation of TNIT concentrations shows good agreement with several measurement studies, given that the lack of post-depositional processing in the model leads to an expected underestimate of maximum values in November through January. Remote NOx sources have the greatest impact May-July, during when the model background concentrations are sensitive to NOx emissions from fossil fuel combustion, soil, and lightning originating from 25°S to 65°S. In this season, NOx is transported to Antarctica as TNIT, which is formed above continental source regions at an altitude of 5-11 km. In other seasons, more NOx is transported as a reservoir species (e.g., peroxyacetyl nitrate, PAN) through the free troposphere, transforming into TNIT within a cone of influence that extends to 35°S and above 4 km altitude. Photolysis of PAN over Antarctica is the main driver of modeled NOx seasonality. Stratospheric production and loss of tracers are relatively unimportant in monthly sensitivities in GEOS-Chem, driving only a few percent of surface level variability of TNIT. A small peak concentration in August is captured by the model, although some measured values in August fall outside the range of simulated concentrations. Modifications to the model to represent sedimentation of polar stratospheric clouds (PSCs) lead to increased surface level August TNIT concentrations. However, this simple representation does not explicitly account for PSC particle deposition or disappearance of the tropopause in the middle of winter, and thus the influence of stratospheric nitrate sources estimated in this study is likely a lower bound.