US EPA

1597427 

Journal Article 

The role of arsenic in Chalcolithic copper artefacts - Insights from Vila Nova de São Pedro (Portugal) 

Pereira, F; Silva, RJC; Soares, AMM; Araújo, MF 

2013 

40 

4 

2045-2056 

10.1016/j.jas.2012.12.015 

WOS:000316709300040 

The Castro of Vila Nova de São Pedro (VNSP) is an emblematic settlement located at Azambuja, Portuguese Estremadura. It was occupied during the third and second millennia BC, predominantly during the Chalcolithic period. A diversified collection of 53 copper-based artefacts (most part in a fragmentary condition), belonging to an extensive metallic collection recovered during excavations carried out in VNSP, was studied using micro-EDXRF spectrometry, optical microscopy and SEM-EDS. Additionally, Vickers microhardness measurements were performed to establish the effectiveness of the thermomechanical treatment in the hardness of the artefacts. Results show that the Largo do Carmo, artefact collection is mainly composed of copper or arsenical copper, being 37% of the artefacts made of copper alloyed with arsenic (As > 2%). A statistically significant association was found between copper alloyed with arsenic and artefacts classified as tools/weapons (arrowheads, daggers and knives). In several cases, the presence of arsenic rich phases in the microstructure, resulting from an inverse segregation phenomenon, shows no evidence of chemical homogeneity control during the artefact manufacture. Microstructural analyses also show that the majority of this group (73%) was shaped with forging plus annealing operation cycles and 23% of the artefacts received a final cold hammering after the forging and annealing. An association between the presence of a final forging treatment and artefacts presenting higher arsenic contents was also identified. Nevertheless, no direct correlation was found between the arsenic content of the alloy and its hardness. Also no direct correlation was found between the hardness and a final forging operation. However, it was observed that a harder forging was applied to the cutting edge of the artefacts and consequently a high hardness in this area was obtained despite the arsenic content of the alloy. Concerning arsenical copper alloys, all evidences point out that the potential for obtaining a harder material was not recognized by the ancient metallurgists and the selection of the alloy was possibly made based on colour. 

Chalcolithic; Elemental composition; Arsenic; Microstructure; Vickers microhardness