Gravitational separation of gases and isotopes in polar ice caps.

Atmospheric gases trapped in polar ice at the firn to ice transition layer are enriched in heavy isotopes (nitrogen-15 and oxygen-18) and in heavy gases (O(2)/N(2) and Ar/N(2) ratios) relative to the free atmosphere. The maximum enrichments observed follow patterns predicted for gravitational equilibrium at the base of the firn layer, as calculated from the depth to the transition layer and the temperature in the firn. Gas ratios exhibit both positive and negative enrichments relative to air: the negative enrichments of heavy gases are consistent with observed artifacts of vacuum stripping of gases from fractured ice and with the relative values of molecular diameters that govern capillary transport. These two models for isotopic and elemental fractionation provide a basis for understanding the initial enrichments of carbon-13 and oxygen-18 in trapped CO(2), CH(4), and O(2) in ice cores, which must be known in order to decipher ancient atmospheric isotopic ratios.