Experimental study of the ageing of building stones exposed to sulfurous and nitric acid atmospheres

During the last few decades, due to remediation procedures, SO2 emissions in the atmosphere have decreased, unlike NOx. Air pollution has changed. Indeed, the aim of this research is to assess the effect of NOx and their interactions with SO2 on stones, particularly on limestones used in Champagne-Ardenne (France) during the restoration processes. Three French building limestones (Courville, Dom and Savonnières) and one reconstituted stone were exposed during 28 days to four strong acid atmospheres i.e. two H2SO3 solutions with different concentrations and two mixed atmospheres with different proportions of HNO3 and H2SO3. These tests produced an intensive acid attack on the stone, allowing the observation of short-term salt precipitation and the evolution of stone properties. Each day, one sample was removed from the acid atmosphere to measure the concentration of SO4(2-) and NO3(-) by ion-chromatography. The surface changes were assessed before and after the tests by 3D scanning and observations with electron microscopy. X-ray microtomography has been performed in the Centre for X-ray Tomography (UGCT) and the Department of Geology at Ghent University (Belgium) in order to observe the penetration of salts and the consequences in stones porosity. First observations showed that exposure to acid atmosphere, led to gypsum efflorescences. Obvious colour changes occurred in all tests. Salt crystallization entailed a change in the porous system, which was evidenced by 3D, mercury porosimetry and X-ray microtomography. Difference between weathered and fresh stone was highlighted by Ion chromatography analyses.