Model study of the first steps in the deterioration of calcareous stone II. Sulphate formation on calcite

The crucial role of surface water in the formation of surface sulphite was addressed in a previous study by in-situ Diffuse Reflectance Infrared Fourier Transform spectrometry (DRIFT). No sulphate was formed, indicating O2(g) to be too weak an oxidant to oxidize surface sulphite. The usefulness of DRIFT is further emphasized as it is employed to investigate the roles of NO2 and O3 in the formation of gypsum on calcareous stone at close to normal atmospheric conditions. Sulphate formation at calcite, employed to model e.g. marble, is shown to progress via a surface sulphite intermediate. NO2 is found to catalyze surface sulphate formation by activating molecular oxygen, while ozone acts to form sulphate by direct oxidation.