Integrated Comprehensive Characterization of Black Crusts from Milan’s Monumental Cemetery: A Synergistic Approach Combining Conventional and Unconventional Analytical Techniques

Black crusts are degradation features found on stone buildings, offering valuable insights into local pollution sources. Their composition and structure reflect environmental conditions, making them important indicators for environmental and conservation studies. In this study, black crusts collected from funerary monuments in the Monumental Cemetery of Milan were comprehensively characterized using SEM-EDX, Raman spectroscopy, LIBS, and oxidative potential (OP) assays. SEM-EDX and Raman spectroscopy revealed extensive degradation of the substrate and the incorporation of pollutant-derived particles, with heavy metals such as Fe, Zn, and Pb detected in more than 90% of the samples. Correlation analysis proved effective in distinguishing major pollution sources, primarily vehicular and railway traffic, indicated by strong associations such as Zn–Mn (r = 0.896), Fe–Zn (r = 0.734), and Fe–Mn (r = 0.655), from minor sources linked to industrial emissions, reflected in correlations including Ti–Pb (r = 0.589), Pb–Cl (r = 0.702), and S–Pb (r = 0.661). Instead, LIBS analysis confirmed stratigraphic penetration of these elements beyond the surface layers, suggesting long-term accumulation. OP assays, applied here for the first time to black crusts, showed values between 0.5 and 3.0 pmol min−1 µg−1, indicating moderate oxidative reactivity linked to metal content. Overall, the findings contribute to a deeper understanding of pollution-driven stone decay and support the development of more effective diagnostic and conservation strategies.