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In this study, Monte Carlo (MC) simulations combined with energy dispersive X-ray fluorescence (EDXRF) spectroscopy have been used to characterize non-destructively a collection of Cu-based artifacts recovered from two archeological sites in southern Portugal: (a) the Chalcolithic E.T.A.R. site of Vila Nova de Mil Fontes and (b) the Middle Bronze Age site of Quinta do Estácio 6. The metal artifacts show a multilayered structure made up of three distinct layers: (a) brownish carbonate soil-derived crust, (b) green oxidized corrosion patina, and (c) bulk metal. In order to assess the reliability of the EDXRF-based Monte Carlo simulations to reproduce the composition of the alloy substrate in archeological bronze artifacts without the need to previously remove the superficial corrosion and soil derived patinas, EDXRF analysis together with scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) was also performed on cleaned and patina-/crust-coated areas of the artifacts. Characterization of the mineralogical composition of the corrosion products in the surface patinas was further determined by means of X-ray diffraction (XRD). Results suggest that the adopted EDXRF/Monte Carlo protocol may represent a safe and fast analytical approach in the quantitative characterization of the bulk chemical composition of Cu-based metal artifacts even in the presence of fairly thick corrosion patinas and/or soil-derived encrustations at the surface of the archeological objects. [ABSTRACT FROM AUTHOR]

This study focusses on the development and application of an innovative protocol which combines chemical data, GIS (geographical information system) and PCA, involving numeric (chemical composition) and categorical (typology of object, archaeological context, chronology and geographical areas) variables, as a simple tool to help in the visualisation and interpretation of large multidisciplinary datasets on Cu-based alloy archaeological artefacts influenced by Phoenician-Punic contacts. The protocol is a useful tool for highlighting existing connections between specific alloy chemical compositions, the location of the original settlement where the artefact had been produced and the proximity to mining resources, waterways, and allochthonous presence such as, in the specific case of this study, the Phoenician and Punic influence in the Iberian bronze production during the Late Bronze Age-Iron Age. The protocol was tested successfully in a case study concerning the precise dating and provenance of bronze statuettes of unknown age and provenance from the Evora Museum collection in Southern Portugal where it confirmed and further refined earlier hypotheses based solely on archaeological and/or chemical studies. The results were interpreted with a unique perspective, to validate the GIS system in combination with experimental chemical-physical data to yield the identification of metallurgical sites of bronze production. [ABSTRACT FROM AUTHOR]