Observations of hydroxyl and the sum of peroxy radicals at Summit, Greenland during summer 2003

The first measurements of peroxy (HO 2+ RO 2) and hydroxyl (OH) radicals above the arctic snowpack were collected during the summer 2003 campaign at Summit, Greenland. The median measured number densities for peroxy and hydroxyl radicals were 2.2×10 8 mol cm −3 and 6.4×10 6 mol cm −3, respectively. The observed peroxy radical values are in excellent agreement ( R 2 = 0.83 , M / O = 1.06 ) with highly constrained model predictions. However, calculated hydroxyl number densities are consistently more than a factor of 2 lower than the observed values. These results indicate that our current understanding of radical sources and sinks is in accord with our observations in this environment but that there may be a mechanism that is perturbing the (HO 2+ RO 2)/OH ratio. This observed ratio was also found to depend on meteorological conditions especially during periods of high winds accompanied by blowing snow. Backward transport model simulations indicate that these periods of high winds were characterized by rapid transport (1–2 days) of marine boundary layer air to Summit. These data suggest that the boundary layer photochemistry at Summit may be periodically impacted by halogens.