EDXRF and micro-EDXRF studies of Late Bronze Age metallurgical productions from Canedotes (Portugal) Pedro Valerio a, * , Maria de Fa ´tima Arau ´jo a , Alexandre Canha b a Instituto Technologico e Nuclear, Chemistry, Estrada Nacional 10, 2686-953 Sacavem, Lisbon, Portugal b Centro de Estudos Pre ´-histo ´ ricos da Beira Alta, Largo Anto ´ nio Jose ´ Pereira, 3501-997 Viseu, Portugal Received 28 May 2007; received in revised form 27 June 2007 Available online 28 August 2007 Abstract Metallurgical production in Central Portugal during the Late Bronze Age was primarily based on copper–tin alloys, despite influences from the Atlantic area where copper–tin–lead alloys are common. Metallic artefacts from archaeological site of Canedotes (Central Por- tugal) were analysed by EDXRF to establish the type of alloys present. Polished spots in selected artefacts were also analysed by micro- EDXRF to determine the major and minor elemental composition of the original alloys. The collection constitutes 18 copper–tin arte- facts and one unalloyed copper artefact with tin and arsenic as minor constituents. Artefacts that require a thermomechanical finishing process, such as tools and weapons, seem to have improved control over the tin content. The composition of two buttons, one cramp and one metallic droplet suggest that some of the copper sources were rich in arsenic. Finally, the low iron content of the artefacts seems to agree well with the smelting of copper ores in crucible furnaces, a smelting process used in certain areas of the Iberian Peninsula until pre- Roman times. Ó 2007 Elsevier B.V. All rights reserved. PACS: 81.05.Bx; 82.80.Ej Keywords: Micro-EDXRF; EDXRF; Archaeometallurgy; Late Bronze Age; Portugal 1. Introduction The Late Bronze Age (LBA) metallurgy in the Mediter- ranean area, including most of the Iberian Peninsula, is characterized by copper–tin alloys while the leaded bronze alloys prevail in the Atlantic area, namely in the British Isles and northwestern regions of France and the Iberian Peninsula [1]. Technological reasons are often stated concerning the addition of lead to copper–tin alloys, namely the reduction of the alloy melting point and the increase of fluidity and time of solidification of the molten alloy. Therefore, leaded bronzes are better suited for mold casting and some authors believe that its introduction is related with the increased use during the LBA of this shaping method over the early process of forging and hammering [2]. The intro- duction of lead can also indicate difficulties in the supply of tin, as was suggested for the northwest of the Iberian Pen- insula [3]. The central region of the Portuguese territory (i.e. region between Tagus and Douro rivers) was one of the main sources of tin in Europe during Antiquity [4]. Significant copper sources seem to be absent in the area. Copper could arrive from nearby regions with important copper mines during ancient times, namely the southern Portuguese ter- ritory [5] or the upper Douro valley [3]. However, we can- not exclude some minor sources of copper, either local [6] or located in the northern Portuguese territory [7], which despite their small size would be sufficient for such LBA minor scale metallurgical operation. The region between Tagus and Douro rivers experienced influences from Atlantic and Mediterranean cultures, noticeable in the presence of artefacts typologically related 0168-583X/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.nimb.2007.07.004 * Tel.: +351 219946207; fax: +351 219946185. E-mail address: pvalerio@itn.pt (P. Valerio). www.elsevier.com/locate/nimb Nuclear Instruments and Methods in Physics Research B 263 (2007) 477–482 NIM B Beam Interactions with Materials & Atoms