Heterogeneous reactions of nitrogen oxides on metal oxide surfaces have been suggested to play a significant role in environmental chemistry, physics, and engineering. Many of the metal oxide compounds found among atmospheric mineral dust particles are inherently semiconducting substrates. Due to their low band gap, they are effective photoactive materials in the environmentally relevant ultraviolet (UVA) range of solar radiation. Here, we have studied nitrogen oxide species evolution and photochemistry on TiO 2 (110) surfaces in the context of atmospheric chemistry by means of near ambient pressure X-ray photoelectron spectroscopy (AP-XPS) coupled with a 375 nm UV-laser module. In the presence of molecular O 2 only, changes in TiO 2 surface potential under UV irradiation were observed, attributed to band flattening. Under humid conditions, a significant increase in the BE range attributed to surface hydroxyl groups was observed, which may be the basis for the light-induced superhydrophilicity observed elsewhere with titania-based nanomaterials. The formation of surface nitrite and nitrate was observed after exposure to NO 2 in the dark. Core-level metal cation, O, and N XPS spectra were measured at elevated pressures of O 2 , NO 2 , and H 2 O. By selective UV irradiation of only the XPS measurement spot on the sample, we obtained differential information on the surface chemical state on the UV-irradiated compared to dark reference spots. Upon UV irradiation, increased oxidation of NO 2 was observed, while in turn a substantial increase of a reduced nitrate species possibly from electron transfer to nitrate and of a further reduced nitrogen species was observed during exposure to UV-radiation. The effect of surface hydroxylation and the involvement of carbon-containing surface compounds in the formation of nitrogenated organic species are emphasized.

Abstract. Release of trace gases from surface snow on earth drives atmospheric chemistry, especially in the polar regions. The gas-phase diffusion of methanol and of acetone through the interstitial air of snow was investigated in a well-controlled laboratory study in the temperature range of 223 to 263 K. The aim of this study was to evaluate how the structure of the snowpack, the interaction of the trace gases with the snow surface, and the grain boundaries influence the diffusion on timescales up to 1 h. The diffusive loss of these two volatile organics into packed snow samples was measured using a chemical ionization mass spectrometer. The structure of the snow was analysed by means of X-ray-computed micro-tomography. The observed diffusion profiles could be well described based on gas-phase diffusion and the known structure of the snow sample at temperatures ≥ 253 K. At colder temperatures, surface interactions start to dominate the diffusive transport. Parameterizing these interactions in terms of adsorption to the solid ice surface, i.e. using temperature-dependent air–ice partitioning coefficients, better described the observed diffusion profiles than the use of air–liquid partitioning coefficients. No changes in the diffusive fluxes were observed by increasing the number of grain boundaries in the snow sample by a factor of 7, indicating that for these volatile organic trace gases, uptake into grain boundaries does not play a role on the timescale of diffusion through porous surface snow. For this, a snow sample with an artificially high amount of ice grains was produced and the grain boundary surface measured using thin sections. In conclusion, we have shown that the diffusivity can be predicted when the structure of the snowpack and the partitioning of the trace gas to solid ice is known.

Surface snow is a chemically active medium (Domine and Shepson, 2002). It exerts a major effect on overall snow chemistry and can alter the composition of the overlying air mass. This in turn can affect air quality and climate (Grannas and others, 2007). Chemically reactive trace gases and impurities are typically located on the surface of ice and in grain boundaries (GBs) (Domine and others, 2008). Field and laboratory measurements have shown that the morphology and surface area (SA) of ice crystals strongly influence trace gas exchange with the atmosphere during snow metamorphism (Domine and others, 2008). The exact role of GBs in snow and ice chemistry, however, is not well understood (Domine and others, 2008; Barret and others, 2011). Earlier work concerning the adsorption of acetone onto packed single-crystalline ice and packed ice beads did not specifically address the role of GBs in surface chemistry (Bartels-Rausch and others, 2004). We define a GB as an interface between two ice crystals aligned in different crystal orientations. The observation that acidic trace gases accumulate along GBs in natural snow has led to the suggestion that GBs provide an extensive surface area for reactions with trace gases and impurities (Mulvaney and others, 1988; Huthwelker and others, 2006). The total

A rotating cylindrical magnetron with a Ti target was sputtered in pure Xe or in a mixture of Xe and N2. The atomic composition of the target surface during sputtering has been investigated by in situ Rutherford backscattering spectrometry. The noble gas atomic ratio at the target surface is around 3.4% or 9.8% for sputtering in pure Xe and with 10% N2 addition, respectively. Energy resolved mass spectrometry reveals that some of the implanted Xe atoms are sputtered from the target. A radiation enhanced diffusion/detrapping/sputtering mechanism is proposed to model the flux of noble gas leaving the target during sputtering.

Release of trace gases from surface snow on Earth drives atmospheric chemistry, especially in the polar regions.

The gas-phase diffusion of methanol and of acetone through the interstitial air of snow was investigated in a well-controlled laboratory study in the temperature range of 223 to 263 K. The aim of this study was to evaluate how the structure of the snowpack, the interaction of the trace gases with the snow surface, and the grain boundaries influence the diffusion on timescales up to 1 h.

The diffusive loss of these two volatile organics into packed snow samples was measured using a chemical ionization mass spectrometer. The structure of the snow was analyzed by means of X-ray computed micro-tomography. The observed diffusion profiles could be well described based on gas-phase diffusion and the known structure of the snow sample at temperatures ≥ 253 K. At colder temperatures surface interactions start to dominate the diffusive transport. Parameterizing these interactions in terms of adsorption to the solid ice surface, i.e. using temperature dependent air–ice partitioning coefficients, better described the observed diffusion profiles than the use of air–liquid partitioning coefficients. No changes in the diffusive fluxes were observed by increasing the number of grain boundaries in the snow sample by a factor of 7, indicating that for these volatile organic trace gases, uptake into grain boundaries does not play a role on the timescale of diffusion through porous surface snow.

In conclusion, we have shown that the diffusivity can be predicted when the structure of the snowpack and the partitioning of the trace gas to solid ice is known