The variations of the fluorescence emission of carmine lake travelling through an absorbing and scattering medium, such as a paint layer, were investigated by ultraviolet (UV)–visible absorption, fluorescence spectroscopy, and imaging techniques. Samples of the lake were studied in dilute and saturated solutions, on a reference test panel and a real case study. Relevant spectral modifications have been observed as a function of the lake concentration mainly consisting of a fluorescence quenching, red shift of emission maxima, and deformation of emission band. The application of a correction factor based on the Kubelka–Munk model allowed fluorescence spectra obtained in solution and on painted samples of known composition to be compared and correlated, highlighting that the fluorescence of the lake within paint layers is affected by both self-absorption and aggregation phenomena. This approach has been successfully applied on a painting by G. Vasari for the noninvasive identification of carmine lake. The results reported here emphasize the necessity of taking physical phenomena into account in the interpretation of the fluorescence spectra for a proper and reliable characterization and identification of painting materials in works of art.

Photo-induced luminescence imaging techniques, such as UV-induced visible luminescence (UVL) and the more recently developed technique of visible-induced infrared luminescence (VIL), have been invaluable for the study of ancient polychromy, allowing the detection and mapping of luminescent materials, such as varnishes, consolidants, organic binders, and crucially, traces of pigments, organic and inorganic, that are often not visible to the naked eye. In the context of works from the Hellenistic period onwards, the detection of two pigments, Egyptian blue and rose madder lake, has been particularly pivotal in advancing the field. Current conventional methodologies for the digital mapping of these two luminescent pigments rely on the separate application of two techniques (VIL and UVL), each requiring a different illumination source and acquisition set-up. In this study, a novel approach is proposed, combining the use of visible-induced infrared luminescence and visible-induced visible luminescence to locate these two pigments. As the source of illumination in both cases is the same system of LEDs, the set-up has the advantage of requiring only minor filter changes between luminescence modes. The increased portability and safety compared to the use of methodologies that employ UV radiation represent notable advantages of this integrated system. The interchangeability between highly selective excitation sources, also significantly simplifies the experimental set-up and the need to adjust the object or equipment between acquisitions, ensuring better reproducibility of the data acquired and facilitating any post-processing procedures. This results in a user-friendly methodology for both experts and non-specialists alike. Three Hellenistic period terracottas; two from Canosa di Puglia, Italy (270–200 BC) and one from Myrina, Turkey (c. 100 BC), all characterised by large well-preserved areas of decoration in Egyptian blue and red lake, were studied in order to trial the approach. Comparisons were made with the more standard techniques of VIL and UVL, and it was shown that the combined method proposed efficiently detects and maps both of these pigments with analogous results to those obtained by more established methodologies. The observations made from the multispectral images acquired were verified by analysis of small samples of the pigments, using FTIR and Raman spectroscopy and HPLC-DAD analysis.