Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 9 2 2009 10.5194/acpd-9-7115-2009 http://www.atmos-chem-phys-discuss.net/9/7115/2009/ http://www.atmos-chem-phys-discuss.net/9/7115/2009/acpd-9-7115-2009.html http://www.atmos-chem-phys-discuss.net/9/7115/2009/acpd-9-7115-2009.pdf 7115 7154 2009-03-17 Kinetics and mechanisms of heterogeneous reaction of NO₂ on CaCO₃ surfaces under dry and wet conditions H. J. Li T. Zhu tzhu@pku.edu.cn D. F. Zhao Z. F. Zhang Z. M. Chen State Key Joint Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing, 100871, China Calcium nitrate (Ca(NO₃)₂) was observed in mineral dust and could change the hygroscopic and optical properties of mineral dust significantly due to its strong water solubility. The reaction of calcium carbonate (CaCO₃) with nitric acid (HNO₃) is believed the main reason for the observed Ca(NO₃)₂ in the mineral dust. In the atmosphere, the concentration of nitrogen dioxide (NO₂) is orders of magnitude higher than that of HNO₃; however, little is known about the reaction of NO₂ with CaCO₃. In this study, the heterogeneous reaction of NO₂ on the surface of CaCO₃ particles was investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) combined with X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) under wet and dry conditions. Nitrate formation was observed in both conditions, and nitrite was observed under wet conditions, indicating the reaction of NO₂ on the CaCO₃ surface produced nitrate and probably nitrous acid (HONO). Relative humidity (RH) influenced both the initial uptake coefficient and the reaction mechanism. 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