Physically based modeling of atmosphere-to-snow-to-firn transfer of H₂O₂ at South Pole

Quantitative interpretation of ice core chemical records requires a detailed understanding of the transfer processes that relate atmospheric concentrations to those in the snow, firn, and ice. A unique, 2 year set of year-round surface snow samples at South Pole and snow pits, with associated accumulation histories, were used to test a physically based model for atmosphere-to-firn transfer of H₂O₂. The model, which extends our previous transfer modeling at South Pole into the snowpack, is based on the advection-dispersion equation and spherical diffusion within representative snow grains. Required physical characteristics of the snowpack, such as snow temperature and ventilation, were estimated independently using established physical models. The surface snow samples and related model simulations show that there is a repeatable annual cycle in H₂O₂ in the surface snow at South Pole. It peaks in early spring, and surface snow concentration is primarily determined by atmospheric concentration and temperature, with some dependence on grain size. The snow pits and associated model simulations point out the importance of accumulation timing and annual accumulation rate in understanding the deposition and preservation of H₂O₂ and δ¹⁸O at South Pole. Long-term snowpack simulations suggest that the firn continues to lose H₂O₂ to the atmosphere for at least 10-12 years (∼3 m) after burial at current South Pole temperatures and accumulation rates.