Shedding new light on historical metal samples using micro-focused synchrotron X-ray fluorescence and spectroscopy

Abstract

Synchrotron-based micro-X-ray fluorescence (micro-XRF) and micro-X-ray absorption spectroscopy (micro-XAS) were used in the present study to obtain spatially resolved micro-scale information on elemental composition, trace element distribution, chemical speciation and oxidation state and/or mineral phase distribution within historical iron artefacts dating from the Iron Age to early Medieval Times. Large area two-dimensional trace element distribution maps and oxidation state maps with micrometer spatial resolution were required to answer open archaeological questions in the context of ancient metal processing. The first set of examples was focusing on historical weapons and included two ancient iron sword blades. The micro-XRF maps revealed a distinct, highly correlated distribution pattern of trace elements such as As, Ni, Cu and Zn. Accordingly, the number of used raw materials could be determined unambiguously and key information concerning the used ancient smithing technique were gained. Further, the ability to record—in a fast manner—large area maps with high spatial resolution (‘elemental screening’) led to the discovery of a hitherto unknown enhanced occurrence of selected trace elements (Cu, Zn, and Au) at the blade surface. Complementary investigations by high resolution scanning electron microscopy were able to localize these trace metals within a carbon-rich matrix may be pointing towards an artifact induced during preservation. A second set of investigated artefacts is dealing with smithing waste products and related historical processing techniques and conditions. Synchrotron-based micro-XRF and micro-XAS were used to determine the structural composition as well as the spatial variation of the predominant Fe oxidation state and corresponding crystallographic phases. The study revealed the presence of distinct domains of Fe 0, Fe IIO (wustite), and α-Fe IIIOOH (goethite), separated by sharp domain boundaries. These findings help to gain new insights concerning the nature and origin of used raw materials as well as regarding employed processing techniques during historic iron fabrication and weapon manufacturing.The study demonstrates the potential of oxidation state and mineral phase mapping based on energy selective micro-XRF maps and spectroscopic phase identification. Such a spatially resolved recording of the chemical speciation is based on X-ray absorption spectroscopy. This analytical technique is exclusive to synchrotron light sources. However, the steadily increasing number of available synchrotron-based X-ray microprobes allows nowadays for more routine utilization of such micro-XAS techniques.