ethene, and propene within surface snow at Summit,

Measurements at Summit, Greenland, performed from June–August 1999, showed significant enhancement in concentrations of several trace gases in the snowpack (firn) pore air relative to the atmosphere. We report here measurements of alkenes, halocarbons, and alkyl nitrates that are typically a factor of 2–10 higher in concentration within the firn air than in the ambient air 1–10m above the snow. Profiles of concentration to a depth of 2m into the firn show that maximum values of these trace gases occur between the surface and 60 cm depth. The alkenes show highest pore mixing ratios very close to the surface, with mixing ratios in the order ethene> propene> 1-butene:Mixing ratios of the alkyl iodides and alkyl nitrates peak slightly deeper in the firn, with mixing ratios in order of methyl> ethyl> propyl: These variations are likely consistent with different near-surface photochemical production mechanisms. Diurnal mixing ratio variations within the firn correlate well with actinic flux for all these gases, with a temporal offset between the solar maximum and peak concentrations, lengthening with depth. Using a snow-filled chamber under constant flow conditions, we calculated production rates for the halocarbons and alkenes that ranged between 103–105 and 106molecules cm3 s1, respectively. Taken together, these results suggest that photochemistry associated with the surface snowpack environment plays an important role in the oxidative capacity of the loca