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A correct determination of the mineral and chemical composition of specimens is of the utmost importance to answer questions regarding the Cultural Heritage field. Because of the preciousness and often very low quantity of sample available, with textures and sizes in the nano-to-micrometric range, scanning electron microscopy (SEM) combined with energy-dispersive X-ray spectroscopy (EDS) is one of the most suited and exploited nano-microanalytical techniques. In these cases, to avoid severe mistakes and quantification errors in SEM-EDS, it is mandatory to consider several effects related to the transport of electrons and X-rays in the material, which in turn are dependent on the SEM-EDS setup. In the present work, a Monte Carlo SEM-EDS nano-microanalytical simulation strategy is proposed and applied to a practical selected case. The Egyptian blue mineral pigment, which is found in Pompeian murals, is used here as an example and model system to show the effects of real size variations (0.1–10 µm), basic geometrical shapes of the pigment (prismatic and spherical) and typical SEM setups, sample holders and substrates. The simulations showed a great—sometimes not intuitive—dependence of the X-ray intensity on the thickness and shape of the samples and SEM-EDS parameters, thereby influencing the analysis and quantification. The critical overview of the results allowed the determination of the correct procedure and technical SEM-EDS parameters and indicated how to apply the Monte Carlo simulation strategy to other Cultural Heritage cases.

Monte Carlo SEM-EDS Nano-Microanalysis Strategy of Historical Mineral Pigments: The Simulation of the Egyptian Blue from Pompeii (Italy) as an Example