No abstract

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. A conventional Langmuir adsorption isotherm describes the uptake in a quantitative manner while dissociative Langmuir isotherms that have been used in the past to model this process do not. The unsaturated surface coverages are strongly temperature dependent, in agreement with a number of field measurements of the nitric acid (or NOy) component of cirrus cloud particles. These laboratory results match those in the field better than do those measured at significantly higher partial pressures but, nevertheless, they still indicate somewhat greater uptake, particularly at higher temperatures.

Abstract. The heterogeneous oxidation of SO 2 by NO 2 on mineral dust was studied using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) and a Knudsen cell. This made it possible to characterise, kinetically, both the formation of sulfate and nitrate as surface products and the gas phase loss of the reactive species. The gas phase loss rate was determined to be first order in both SO 2 and NO 2 . From the DRIFTS experiment the uptake coefficient, γ , for the formation of sulfate was determined to be of the order of 10 −10 using the BET area as the reactive surface area. No significant formation of sulfate was seen in the absence of NO 2 . The Knudsen cell study gave uptake coefficients of the order of 10 −6 and 10 −7 for SO 2 and NO 2 respectively. There was no significant difference in uptake when SO 2 or NO 2 were introduced individually compared to experiments in which SO 2 and NO 2 were present at the same time.

The interactions of gas-phase acetone, ethanol and benzene with smooth ice films and artificial snow have been studied. In one technique, the snow is packed into a cylindrical column and inserted into a low-pressure flow reactor coupled to a chemical-ionization mass spectrometer for gas-phase analysis. At 214 and 228 K, it is found for acetone and ethanol that the adsorbed amounts per surface area match those for adsorption to thin films of ice formed by freezing liquid water, when the specific surface area of the snow (as determined from Kr adsorption at 77 K) and the geometric surface area of the ice films are used. This indicates that freezing thin films of water leads to surfaces that are smooth at the molecular level. Experiments performed to test the effect of film growth on ethanol uptake indicate that uptake is independent of ice growth rate, up to 2.4 μm min −1 . In addition, traditional Brunauer-Emmett-Teller (BET) experiments were performed with these gases on artificial snow from 238 to 266.5 K. A transition from a BET type I isotherm indicative of monolayer formation to a BET type II isotherm indicative of multilayer uptake is observed for acetone at T 263 K and ethanol at T 255 K, arising from solution formation on the ice. When multilayer formation does not occur, as was the case for benzene at T 263 K and for acetone at T 255 K, the saturated surface coverage increased with increasing temperature, consistent with the quasi-liquid layer affecting adsorption prior to full dissolution/multilayer formation.