João Pedro Veiga

This paper presents a comprehensive study of the evidence for ancient tin mining at the Ervedosa mine (Vinhais, Portugal). The geological context of the site indicates a rich cassiterite (SnO2) deposit, which was subject to mining in the twentieth century. Some ancient mining and ore processing stone tools were recovered during the twentieth century mining operations, namely one hammer, one pounder, one flat anvil and five small tools used both as pounders and crushing anvils, evidencing prehistoric mining activities. XRF and SEM–EDS chemical analyses were performed on primary and secondary cassiterite samples from the mining site, demonstrating the abundance and chemical heterogeneity of the tin (Sn) ores. The stone tools can be ascribed to Bronze Age or, at the latest, Early Iron Age (2nd millennium to the first half of 1st millennium BCE) by comparison with similar tools from other Iberian and European archaeological contexts. High-resolution photogrammetric 3D models of the tools are made available in this study. The historical descriptions of the findings and the research made on the technical archives about the mine allowed correlating the tools to mining in a primary context, focused on rich quartz veins in granitic or greisen bedrock, rather than mining in a secondary context. XRF and SEM–EDS analyses performed on the stone material and on surface adherences support their identification as specific types of hard rocks, such as granite, amphibolite and quartzite, and allowed the detection of Sn-rich adherent particles, confirming their use for Sn-material processing. The potential relation between the cassiterite resources and the local later prehistoric (Bronze Age to Early Iron Age) settlement pattern is also discussed. The results raise awareness and provide relevant data about the existence of tin mining in primary contexts during later prehistoric times in the NW Iberian Peninsula.

Sol-gel production of hybrid materials has, to some extent, revolutionised materials’ engineering and the way science and technology perceive the creation of new materials. Despite that, the method presents some limitations that are circumvented by radiation processing. Electron beam irradiation was used to promote synthesis of hybrid structures while using silanol-terminated PDMS, TEOS and TPOZ as precursors. Evaluation of the method’s performance was executed by gel fraction determination, WDXRF and FTIR-ATR. Results showed that, although there is some pre-irradiation reactivity between precursors, radiolysis induces scission on multiple sites of precursor’s structures, which induces hybrid network formation to a greater extent. Characterisation allowed determining electron beam irradiation to be effective in the creation of Si–O–Zr bonds, resulting in the production of a Class II hybrid material.

Findings of Iron Age metallurgical activities related to tin metal and mining are very rare. In the present work, we present a detailed study of the Outeiro de Baltar hillfort, dated to the Late Iron Age/Early Roman period, located in a place where 20th century tin mining work took place. Elemental and microstructural analysis by portable, micro and wavelength dispersive X-ray fluorescence spectrometry (pXRF, micro-XRF and WDXRF) and scanning electron microscopy with energy dispersion spectrometer (SEM-EDS) showed that metallurgical debris found at the archaeological site is related to tin smelting and binary and ternary bronze productions. Analysis of the artefacts of diverse typologies found at the site showed that a variety of metals and alloys were in circulation and use. Samples of tin ores (cassiterite) from the region were analyzed for comparison with an archaeological tin slag from the site. The analytical results point to the production of tin metal using local cassiterite and the production of bronze by directly adding cassiterite into a smelting process. Furthermore, data of remote sensing (airborne Light Detection and Ranging (LiDAR) and historical aerial imagery) and Geographical Information System (GIS) mapping were combined with archival mining documentation and maps to retrieve a landscape context for the site. The study showed that the place of the Outeiro de Baltar hillfort (NW Iberia) was mined periodically over time.

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