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The first part of this study reports on the wide campaign for the extension of the database of both trace and minor elements concentration in diopside by means of μ-PIXE measurements and of luminescence spectra in diopside and wollastonite by means of μ-IL measurements. Diopside and wollastonite are actually two of the most common lapis lazuli-forming minerals. For this former part of the study, we analysed rocks of known provenance at the microbeam line of the LNL laboratories in Legnaro (PD) of the Istituto Nazionale di Fisica Nucleare (INFN). The latter part of the paper is dedicated to the non-invasive Ion Beam Analyses (IBA) characterisation of six pieces of the “Collezione Medicea”. The collection is exhibited at the Museum of Natural History (University of Firenze) and belonged to the Medici family. It includes artworks made of lapis lazuli manufactured in the 16 th and 17 th centuries but there is not precise information about the provenance of the used raw material. Results on the artworks show, as expected, that the Chilean provenance of the material used for the analysed artworks has to be excluded. Lapis lazuli used for five of the analysed artworks can be ascribed to the Afghan quarry district, while one object cannot be attributed only on the base of diopside and wollastonite analysis. [ABSTRACT FROM AUTHOR]