Abstract: An acquisition campaign of macro-X-ray fluorescence scanning measurements on the vault of the Loggia of Cupid and Psyche, frescoed by Raphael and his workshop in the Villa Farnesina (Rome), supplied the occasion of testing the potentialities for such diagnostic tool/technique in studying wall paintings in situ. In this paper, the methodological approach is considered in depth, to highlight significant problematics deriving from nature of materials, painting technique and spatial peculiarities of this kind of artwork, as well as from the treatment and decoding of raw data. Data obtained through a single-spot XRF campaign, carried out during the past restorations of the Loggia, have been considered for comparisons. Graphical abstract: [Figure not available: see fulltext.]. © 2018, Accademia Nazionale dei Lincei.

cited By 0; Article in Press