A new approach to assess the chemical composition of powder deposits damaging the stone surfaces of historical monuments.

The issue of conservation of the monumental heritage worldwide is mainly related to atmospheric pollution that causes the degradation of stone surfaces. The powder deposits present on the stone monuments reflect the composition of the aerosol particulate matter (PM) to which the surfaces are exposed, so the chemical characterization of the outermost damaged layers is necessary in order to adopt mitigation measurements to reduce PM emissions. In the present paper, a new analytical approach is proposed to investigate the chemical composition of powder deposits present on Angera stone, a dolomitic rock used in the Richini courtyard, a masterpiece of Lombard Baroque and placed in Milan. Inorganic and organic components present in these deposits have been analyzed by IC (ion chromatography) and a new approach mainly bases on thermal analyses, respectively. Gypsum is the main inorganic constituent indicating a composition similar to that of black crusts, hard black patina covering the degraded building surfaces. Ammonium nitrate present in the powder is able to react with the stone substrate to form magnesium nitrate which can migrate into the porous stone. The carbonaceous fraction powder deposits (i.e. OC = Organic Carbon and EC = Elemental Carbon) have been quantified by a new simple thermal approach based on carbon hydrogen nitrogen (CHN) analysis. The presence of high concentration of EC confirms that the powder deposits are evolving to black crust. Low values of water-soluble organic carbon (WSOC, determined by total organic carbon-TOC), with respect to what is normally found in PM, may indicate a migration process of organic substances into the stone with a worsening of the conservation conditions. The presence of heavy metals of anthropogenic origin and acting as catalysts in the black crust formation process has been highlighted by SEM-EDS (electron microscopy coupled with an energy dispersive spectrometer) as well.