Multiphase modeling of nitrate photochemistry in the quasi-liquid layer (QLL): implications for NO_x release from the Arctic and coastal Antarctic snowpack

Abstract

Abstract. We utilize a multiphase model, CON-AIR (Condensed Phase to Air Transfer Model), to show that the photochemistry of nitrate (NO3−) in and on ice and snow surfaces, specifically the quasi-liquid layer (QLL), can account for NOx volume fluxes, concentrations, and [NO]/[NO2] (γ=[NO]/[NO2]) measured just above the Arctic and coastal Antarctic snowpack. Maximum gas phase NOx volume fluxes, concentrations and γ simulated for spring and summer range from 5.0×104 to 6.4×105 molecules cm−3 s−1, 5.7×108 to 4.8×109 molecules cm−3, and ~0.8 to 2.2, respectively, which are comparable to gas phase NOx volume fluxes, concentrations and γ measured in the field. The model incorporates the appropriate actinic solar spectrum, thereby properly weighting the different rates of photolysis of NO3− and NO2−. This is important since the immediate precursor for NO, for example, NO2−, absorbs at wavelengths longer than nitrate itself. Finally, one-dimensional model simulations indicate that both gas phase boundary layer NO and NO2 exhibit a negative concentration gradient as a function of height although [NO]/[NO2] are approximately constant. This gradient is primarily attributed to gas phase reactions of NOx with halogens oxides (i.e. as BrO and IO), HOx, and hydrocarbons, such as CH3O2.