Hydroxyl concentration estimates in the sunlit snowpack at Summit, Greenland

Experiments were performed at Summit, Greenland (72°34′ N, 38°29′ W) to investigate hydroxyl mixing ratios in the sunlit surface snowpack (or firn). We added a carefully selected mixture of hydrocarbon gases (with a wide range of hydroxyl reactivities) to a UV and visible light transparent flow chamber containing undisturbed natural firn. The relative decrease in mixing ratios of these gases allowed estimation of the lower limit mixing ratio of hydroxyl radicals in the near-surface firn pore spaces. Hydroxyl mixing ratios in the firn air followed a diurnal cycle in summer 2003 (10–12 July), with peak values of more than 3.2×106 moleculescm−3 between 13:00 and 16:00 local time. The minimum value estimated was 1.1×106 moleculescm−3 at 20:00 local time. Results during spring of 2004 showed lower, but rapidly increasing, peak hydroxyl mixing ratios of 1.1×106 moleculescm−3 in the early afternoon on 15 April and 1.5×106 moleculescm−3 on 1 May. Our firn hydroxyl estimates were similar to directly measured above-snow ambient levels during the spring field season, but were only about 30% of ambient levels during summer.