A by-product of energy-dispersive X-ray fluorescence (EDXRF)-analysis consists of using the ratios of selected X-ray peaks to determine the thickness of multilayered objects. Three different methods were developed in the past, all because the two main K or L X-lines from an EDXRF spectrum emitted by a chemical element have a distinct energy and are differently attenuated by an overlying layer. This specific subject has many papers dedicated, but only a few considerations were devoted to the limits of these methods, that is, the range, for example, of gold thickness that can be usefully determined by each method. This paper defines these limits in the specific case of thin gilding (with d < 1 μm). Three typical situations were considered, and the following artefacts were studied: two artefacts on gilded lead, where the gold leaf is superimposed to a white lead pigment, both in the painting “La Fornarina” of Raphael, dated 1520 AD, and in the imperial carriage of Dom Pedro II emperor of Brazil. In this last case, the white lead pigment was painted over the wood structure of the carriage; four artefacts on gilded copper, three crowns and a pendant, from the tomb of the Lady of Cao, from the Moche civilization of the North of Peru, dated around 350 AD; finally, an artefact on gilded silver, a vase from the Chavín civilization of the North of Peru, dated around 1000-200 BC.
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