Analysis of the surface of different marbles by X-ray photoelectron spectroscopy (XPS) to evaluate decay by SO2 attack

Atmospheric pollution is one of the main agents of decay in monuments and other works of art located in industrialised urban centres. SO2 is a permanent and abundant component of air pollution and, although it does not have an immediate visual effect, after continuous exposure, it can cause irreversible damage to building materials. Marble is one of the most commonly used ornamental stones in historical monuments and its mineralogical composition makes it very susceptible to damage caused by exposure to SO2. To measure the chemical reactions caused on marble by the action of atmosphere rich in SO2, selected calcitic and dolomitic samples were altered by weathering accelerated test. For this, seven marble types (four calcitic and three dolomitic) were exposed to high concentration of sulphur dioxide for 24 h in a climate chamber under controlled temperature and humidity conditions (20 °C and > 90 % HR). Changes on marble surfaces caused by reactions of SO2 with calcite and dolomite were studied using two non-destructive techniques: chromatic change by means of colorimetry and chemical analysis using X-ray photoelectron spectroscopy (XPS). The development of new mineral phases was also observed by scanning electron microscopy. Colorimetric analysis revealed a decrease in lightness and chromatic parameters suggesting that these changes were due to the development of new mineral phases in all marbles. The XPS technique, which is generally used in the analysis of metals, is relatively new in the field of stone deterioration. It enabled us to recognise the development of sulphites and sulphates on marble surfaces with high precision, after just 24 h of exposure to high SO2 concentrations and to distinguish different decay paths for calcitic and dolomitic marbles.