1UPMC Univ. Paris 06, UMR8190, CNRS/INSU − Université Versailles St.-Quentin, LATMOS-IPSL, Paris, France
2University of California, Los Angeles; Department of Atmospheric and Oceanic Sciences, Los Angeles, CA 90095, USA
3Institute for the Study of Earth, Oceans and Space, University of New Hampshire, Durham, NH 03824, USA
4School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA 30033, USA
5Department of Geosciences, University of Houston, TX 77204, USA
6School of Environmental Sciences, University of East Anglia, Norwich, NR4 7TJ, UK
Abstract. The chemical composition of the boundary layer in snow covered regions is impacted by chemistry in the snowpack via uptake, processing, and emission of atmospheric trace gases. We use the coupled one-dimensional (1-D) snow chemistry and atmospheric boundary layer model MISTRA-SNOW to study the impact of snowpack chemistry on the oxidation capacity of the boundary layer. The model includes gas phase photochemistry and chemical reactions both in the interstitial air and the atmosphere. Chemistry on snow grains is simulated assuming a liquid-like layer (LLL), treated as an aqueous layer on the snow grain surface. The model has been recently compared with BrO and NO data taken on 10 June–13 June 2008 as part of the Greenland Summit Halogen-HOx experiment (GSHOX). In the present study, we use the same focus period to investigate the influence of snowpack derived chemistry on OH and HOx + RO2 in the boundary layer. We compare model results with chemical ionization mass spectrometry (CIMS) measurements of the hydroxyl radical (OH) and of the hydroperoxyl radical (HO2) plus the sum of all organic peroxy radicals (RO2) taken at Summit during summer 2008. Using sensitivity runs we show that snowpack influenced nitrogen cycling and bromine chemistry both increase the oxidation capacity of the boundary layer and that together they increase the mid-day OH concentrations by approximately a factor of 2. We show for the first time, using an unconstrained coupled one-dimensional snowpack-boundary layer model, that air-snow interactions impact the oxidation capacity of the boundary layer and that it is not possible to match measured OH levels without snowpack NOx and halogen emissions. Model predicted HONO compared with mistchamber measurements suggests there may be an unknown HONO source at Summit. Other model predicted HOx precursors, H2O2 and HCHO, compare well with measurements taken in summer 2000. Over 3 days, snow sourced NOx contributes an additional 2 ppb to boundary layer ozone production, while snow sourced bromine has the opposite effect and contributes 1 ppb to boundary layer ozone loss.