A multi-analytical non-destructive testing (NDT) methodology was applied to copper-based artifacts originated from various archaeological sites of Greece. X-ray fluorescence (XRF), fiber optics diffuse reflectance spectroscopy (FORS) and scanning electron microscopy coupled with an energy dispersive X-ray detector (ESEM-EDX) were used for the characterization of the alloys and the corrosion products. The key elements of the artifacts belonging to the Early Bronze Age (2700–2300 BC) were copper and arsenic, while tin bronze was used for the fabrication of the Late Bronze Age (1600–1100 BC) artifacts. The effectiveness of XRF for the determination of the bulk composition was confirmed by comparative study with the previously applied atomic absorption spectroscopy (AAS) and inductively coupled plasma–atomic emission spectrometry (ICP-AES) destructive techniques. Significant differences between the artifacts were revealed through the spectral measurement of their surface corrosion products color by FORS. ESEM-EDX provided information on the microstructure, the elemental composition of the corrosion layers and bulk, as well as the distribution of the corrosion products on the surface. Conclusively, the combined NDT methodology could be regarded as a valuable and appropriate tool for the elemental composition of the bulk alloy, thus leading to the classification of their historical period and the corrosion products, contributing significantly to their conservation–restoration.
