Background: For more than a decade, Energy Dispersive X-Ray Fluorescence (EDXRF) spectrometry is the primary analytical technique in archaeometric research and especially in the study of ancient copper artefacts. EDXRF has established itself as the fundamental archaeometric analytical technique because of features like: the ability to analyze samples in a non destructive or non invasive way, no requirements for sample preparation, portability, in situ analysis, simultaneous determination of many elements and finally its easy in use. At the same time there is an explosion of related research publications which provide new possibilities to museums and archaeology scientists. On the other hand, due to its limitations it cannot provide information for every analytical question. Objective: The goal of this article is to present an overview of the capabilities of the contemporary EDXRF spectrometry for the study of ancient copper artifacts and the necessity to be implemented, depending on the analytical question, in correlation with complementary analytical techniques which are presented through related case studies. Conclusion: The demand for studying artefacts in situ, the evolution of the instrumentation and the access of more scientists (historians, archaeologists, curators etc.) to archaeometry will maintain EDXRF spectrometry as the central analytical technique. Limitations like inability for light elements detection, penetration depth, low (relatively) sensitivity can be partially overcome with the implementation of other analytical techniques which will provide complementary information. Moreover, progress in non-invasive analysis and new portable instruments combining elemental and molecular techniques expand significantly the capabilities of in situ analysis.

This work describes a holistic archaeometric approach to ancient Macedonian specimens. In the region of the ancient city Lete, the deceased members of a rich and important family were interred in a cluster of seven tombs (4th century BC). Among the numerous grave goods, there was also a set of metal containers preserving their original content. The physico-chemical analysis of the containers and their contents was performed in order to understand the purpose of their use. For the containers, Energy Dispersive micro-X-Ray Fluorescence (EDµXRF) spectroscopy was implemented taking advantage of its non-invasive character. The case (B35) and the small pyxis (B37) were made of a binary Cu-Sn alloy accompanied by a slight amount of impurities (Fe, Pb, As) and the two miniature bowls were made of almost pure Cu. For the study of the contents, a combination of EDµXRF, X-Ray Diffraction (XRD), and Gas Chromatography-Mass Spectrometry (GC-MS) was carried out. Especially for the extraction of the volatile compounds, the Solid Phase Micro-Extraction (SPME) technique was used in the headspace mode. Because of the detection of Br, High Pressure Liquid Chromatography coupled to a Diode-Array-Detector (HPLC-DAD) was implemented, confirming the existence of the ancient dye shellfish purple (porphyra in Greek). The analytical results of the combined implementation of spectrometric and chromatographic analytical techniques of the metal containers and their contents expand our knowledge about the pharmaceutical practices in Macedonia during the 4th century BC.

The chemical composition of 61 copper alloy vessels was studied non-invasively by energydispersive micro-X-ray fluorescence (EDμXRF) spectrometry. The vessels were found in five tombs (A, B, D, Z and H) at Derveni in central Macedonia, Greece, which belong to the cemetery of the ancient city of Lete. The tombs are dated to the last quarter of the fourth century BCE. The opulence of the numerous grave offerings denotes the high social status of the deceased within Macedonian society. The material under study was divided into two main groups according to their appearance and use. The first group included 44 vessels with a golden appearance for use in banquets; the second group consisted of 17 dark vessels for domestic use. The aim of this research was to study the vessels' technology according to their chemical composition. Both golden and dark vessels consisted of a binary Cu-Sn alloy and a slight amount of impurities (Fe, Ni, Zn, Pb, As, Co, Sb, Ag, Ti). It is probable that during construction the ancient metalsmiths were taking into account criteria such as the desired appearance, cost of metals, future use and physical properties such as resistance to corrosion. Banquet vessels had a consistent chemical composition in all their different parts compared with those for domestic use. The only chemical element used systemically for alloying purposes, except Sn, was Pb in order to improve the castability of the bases and handles of the vessels. The study provides additional information about the metalworking of bronzes in central Macedonia in the fourth century BCE, as well as about the access Macedonian metalworkers had at the time to the raw materials for such use.

Un microcosme de couleur et d'éclat. La polychromie des lits de banquets chryséléphantins de la Macédoine antique