| Summary: | We present data collected from a number of snow-covered environments including two polar locations (Summit, Greenland and the South Pole) and two mid-latitude regions (a remote site in northern Michigan, and Niwot Ridge, Colorado). At each site, concentrations of CH3 I and C2 H5 I were enhanced within the interstitial air near the snow surface, compared to levels in boundary layer air. Fluxes of CH3 Br from surface snow to the atmosphere were observed at each site except Niwot Ridge, where CH3 Br appeared to have a sink. The mid-latitude sites showed significant emissions of CH3 Cl, mostly originating at the ground surface and traveling up through the snow, while at the polar locations CH3 Cl emissions from firn air were relatively small. In general, methyl halide mixing ratios in firn air were significantly greater at Summit than at the South Pole, with Summit showing a strong diurnal cycle in the production of alkyl halides that was well correlated with actinic radiation and firn temperature. We suggest that the most likely route to alkyl halide formation is through an acid catalyzed nucleophilic substitution of an alcohol type function by a halide, both of which should be preferentially segregated to the quasi-liquid layer at the surface of the snow grains. A series of experiments using a snow-filled quartz chamber irradiated by natural sunlight allowed estimation of emission trends that were hard to measure in the natural snowpack. These static chamber experiments confirmed significant production of the primary alkyl halides, following the order CH3 Cl > CH3 Br > C2 H5 Cl > CH3 I > C2 H5 Br > C2 H5 I > 1 - C3 H7 Br > 1 - C3 H7 I. Our observations at all four locations, including polar and mid-latitude sites, imply that alkyl halide production may be associated with all surface snows. © 2007 Elsevier Ltd. All rights reserved.
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