Burial of gas-phase HNO(3) by growing ice surfaces under tropospheric conditions.

The uptake of gas-phase nitric acid by ice surfaces undergoing growth by vapor deposition has been performed for the first time under conditions of the free troposphere. The investigation was performed using a coated-wall flow tube coupled to a chemical ionization mass spectrometer, at nitric acid partial pressures between 10(-7) and 10(-6) hPa, at 214, 229 and 239 K. Ice surfaces were prepared as smooth ice films from ultra-pure water.

A kinetic model for uptake of HNO3 and HCl on ice in a coated wall flow system.

A simple model of gas flow and surface exchange with a single site Langmuir mechanism has been developed to describe effects of adsorption and desorption on trace gas concentrations at the outflow from a coated wall flow tube reactor. The model was tested by simulating experimental results for the uptake of HNO3 and HCl on ice films at temperatures and gas concentrations corresponding to the ice stability region in the upper troposphere. The experimental time-dependent uptake profiles were best fitted with an additional process involving diffusion of the adsorbed molecules into the ice film.

Uptake of gas-phase nitric acid to ice at low partial pressures: evidence for unsaturated surface coverage.

The adsorption of gas-phase nitric acid onto water-ice surfaces at temperatures between 200 and 239 K has been studied over short time scales using a coated-wall flow tube coupled to a chemical ionization mass spectrometer. The nitric acid partial pressures used were between 10(-8) hPa and 10(-6) hPa, making this the first systematic study under partial pressure conditions present in the upper troposphere. Whereas previous findings using this technique have shown that the surface coverages are saturated at 2 to 3 x 10(14) molecules cm(-2) (referenced to the geometric surface area of the ice film) when partial pressures are larger than about 10(-7) hPa, the principal finding from this study is that the surface coverages are in the unsaturated regime at lower partial pressures.