Bromide and Other Ions in the Snow, Firn Air, and Atmospheric Boundary Layer at Summit During GSHOX

Measurements of gas phase soluble bromide in the boundary layer and in firn air, and Br- in aerosol and snow, were made at Summit, Greenland as part of a larger investigation into the influence of Br chemistry on HOx cycling. The soluble bromide measurements confirm that photochemical activation of Br- in the snow causes release of active Br to the overlying air despite trace concentrations of Br- in the snow (means 15 and 8 nmol Br- kg-1 of snow in 2007 and 2008, respectively). Mixing ratios of soluble bromide above the snow were also found to be very small (mean < 1 ppt both years, with maxima of 3 and 4 ppt in 2007 and 2008, respectively), but these levels clearly impact Hg speciation and may perturb HOx partitioning. Concentrations of Br- in surface snow tended to increase/decrease in parallel with the specific activities of the aerosol-associated radionuclides 7Be and 210Pb. Earlier work has shown that ventilation of the boundary layer causes simultaneous increases in 7Be and 210Pb at Summit, suggesting there is a pool of Br- in the free troposphere above Summit in summer time. Speciation and the source of this free tropospheric Br- are not well constrained, but we suggest it may be linked to extensive regions of active Br chemistry in the Arctic basin which are known to cause ozone and mercury depletion events shortly after polar sunrise. If this hypothesis is correct, it implies persistence of the free troposphere Br- for several months after peak Br activation in March/April. Alternatively, there may be a ubiquitous pool of Br- in the free troposphere, sustained by currently unknown sources and processes.