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Abstract In this paper, we report a few examples showing how energy dispersive XRF analysis (EDXRF) coupled with visible reflectance spectroscopy (vis‐RS) can be successfully applied for the investigation of wood or canvas paintings by performing stratigraphic analyses with non‐invasive techniques. The specific aim is to reconstruct layers and their thicknesses. The method has been tested in the laboratory on paint layers similar to traditional Renaissance ones. In situ analyses of a famous wood painting by Andrea Mantegna—‘Madonna col bambino e un coro di cherubini’, Pinacoteca di Brera, Milan—were also carried out. While illustrating the results concerning the identification of pigments and the discrimination of layer stratigraphy, advantages and limitation of this method are pointed out. Copyright © 2007 John Wiley & Sons, Ltd.
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