Natural and anthropogenic sources of total suspended particulate and their contribution to the formation of black crusts on building stone materials of Catania (Sicily)

Blackening and disaggregation of exposed surfaces of stone monuments are well-known effects of stone decay taking place in polluted urban environments all over the world. This paper aims to assess the contribution of natural and anthropogenic sources of total suspended particulate (TSP) causing permanent damage (black crusts) to the stone monuments of Catania (Sicily), one of the most popular ‘‘cities of art’’ of southern Italy. Atmospheric pollution of Catania, a typical Mediterranean coastal town, is mainly contributed by vehicle exhaust emissions rather than industrial ones. Episodically, the city also suffers gaseous and ash emissions (plumes) from the nearby Mount Etna volcano. Thus, to discriminate between natural and anthropogenic contributions to stone decay on Catania monuments, black crusts and TSP were sampled within the urban area and subjected to specific analytical procedures (optical microscopy, X-ray powder diffraction, Fourier transformed infrared spectroscopy, scanning electron microscopy equipped with energy dispersive spectrometry, ionic chromatography and dual inlet mass spectrometry). Mineralogical, chemical and isotopic characterization of black crusts and TSP provided new insights concerning the partition of sulfate sources in this particular urban context. The influence of Mount Etna emissions on both TSP and black crusts compositions was shown. Nevertheless, the key role of anthropogenic sources in the total sulfate budget was confirmed, while sea spray and volcanic emissions were found to make subordinate contributions. Quantitative data useful for the identification of the threshold pollution levels for preventive conservation of Catania monuments were obtained.