Macroscopic X-ray fluorescence analysis (MA-XRF) is a non-destructive analytical technique that allows for the rapid and thorough investigation of paintings; therefore, it is nowadays increasingly involved in relevant studies. In the present work, a state-of-the-art MA-XRF set-up is utilized to identify the painting materials and techniques and document the state of preservation of an early 19th-century AD Greek religious panel painting (“icon”). The artifact in consideration has received extensive restoration interventions in the past and is considerably decayed; for these reasons, the interpretation of the relevant MA-XRF elemental intensity distribution maps is challenging. In this framework, it is demonstrated how the elemental distribution maps can be explored and interpreted to lead to a thorough investigation of the painting in consideration. In particular, the MA-XRF data interpretation allowed for the identification of the original palette that includes the rather rarely employed–in icon painting-yellow lead-antimonate pigment, led to the spotting of an invisible inscription, to the documentation of the preparation/gesso layer and the preliminary drawing. Additionally, it was possible to discriminate between the original painting and the later interventions, while the collected data revealed that the painting originally had two cross-bars attached to its back. Ultimately, the presented case study can be utilized as a guide for the proper interpretation of MA-XRF data from decayed and altered icons.
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