Evidence of reactive iodine chemistry in the Arctic boundary layer

Although it has recently been established that iodine plays an important role in the atmospheric chemistry of coastal Antarctica, where it occurs at levels which cause significant ozone (O-3) depletion and changes in the atmospheric oxidising capacity, iodine oxides have not previously been observed conclusively in the Arctic boundary layer (BL). This paper describes differential optical absorption spectroscopy (DOAS) observations of iodine monoxide (IO), along with gas chromatographic measurements of iodocarbons, in the sub-Arctic environment at Kuujjuarapik, Hudson Bay, Canada. Episodes of elevated levels of IO (up to 3.4 +/- 1.2 ppt) accompanied by a variety of iodocarbons were observed. Air mass back trajectories show that the observed iodine compounds originate from open water polynyas that form in the sea ice on Hudson Bay. A combination of long-path DOAS and multiaxis DOAS observations suggested that the IO is limited to about 100 m in height. The observations are interpreted using a one-dimensional model, which indicates that the iodocarbon sources from these exposed waters can account for the observed concentrations of IO. These levels of IO deplete O-3 at rates comparable to bromine oxide (BrO) and, more importantly, strongly enhance the effect of bromine-catalyzed O-3 depletion in the Arctic BL, an effect which has not been quantitatively considered hitherto. However, the measurements and modeling results indicate that the effects of iodine chemistry are on a much more localized scale than bromine chemistry in the Arctic environment.