Efficiency of Portable X-ray Fluorescence for Distinguishing Lead Slag

In the Minier Valley (France, Aveyron), an archaeological site excavation has led to the discovery of 25 kg of lead (Pb) slag, found in a secondary position. On a macroscopic level, these slags can be classified into two distinct categories, vitreous black and porous gray. This clear visual differentiation has been previously documented at other Pb-silver (Ag) metallurgy sites dating from the 12th century to the 14th century in Europe, and more particularly in the workshops of Mont Lozère, located approximately 80 km away from Le Minier. However, to date, scant evidence exists regarding the specific metallurgical process that produced this slag. This study presents the results of the analysis of 218 Pb slags (Supplemental Material) using portable X-ray fluorescence (pXRF). This method does not appear to be ideally suited for investigating this type of artifact, as it does not provide quantification of oxygen content. Nevertheless, it can be used to quickly identify trends and determine whether the two identified facies exhibit dissimilar chemical compositions. The results indicate that, based on the elemental compositions of the slags, no discernible distinction can be made to categorize them into two separate groups, both in bivariate and multivariate analyses. Consequently, it can be inferred that the gray and black slags originate from a single process executed within the same type of furnace. Scanning electron microscopy energy dispersive spectrometry analyses on selected samples demonstrate that variations in metal content are considerably exaggerated by pXRF, but that the trends observed are confirmed. The use of pXRF is therefore a relevant tool for determining whether or not Pb-Ag slag is the result of the same process. However, this initial approach needs to be refined by other analyses to confirm whether the smelted ores are of local origin and to be able to better define the details of the metallurgical process used.