Surface analysis of ancient glass artefacts with ToF-SIMS: A novel tool for provenancing? F.J.M. Rutten a, * , M.J. Roe b , J. Henderson c , D. Briggs a a Centre for Surface Chemical Analysis and Laboratory of Biophysics and Surface Analysis, School of Pharmacy, The University of Nottingham, Nottingham NG7 2RD, UK b School of Mechanical, Materials and Manufacturing Engineering, The University of Nottingham, Nottingham NG7 2RD, UK c Department of Archaeology, School of Humanities, The University of Nottingham, Nottingham NG7 2RD, UK Received 12 September 2005; accepted 15 February 2006 Available online 18 May 2006 Abstract Scientific analysis of ancient glass artefacts has the potential to reveal a great deal of information about ancient manufacturing techniques and trade relations between ancient civilisations. In this paper we applied ToF-SIMS to gain unique knowledge about the presence of a range of (trace) elements in the matrix and micron-sized inclusions in opaque glasses dated to the 14th century BC found at sites in the Middle East and Egypt. Establishment of a careful multi-technique analysis protocol allowed the detection of a range of elements not previously found in such inclusions by other techniques. Comparison with data acquired from a glass standard reference sample has, moreover, enabled quantification of major and trace elements in the glass matrix. It is hoped that this may yield important additional identifying information to assist in provenancing ancient glass artefacts as well as provide new information about the ancient technologies used to produce them. # 2006 Elsevier B.V. All rights reserved. Keywords: ToF-SIMS; Imaging; Archaeometry; Ancient glass; Opacifier 1. Introduction To understand the structure of ancient civilisations and their interactions, archaeological information is often crucial in establishing the existence of ancient trading routes and also production centres for which any written evidence no longer exists. Ancient glass has enormous potential to aid these investigations, but at present it is only rarely possible to provenance glass scientifically to the location of its production. Glass manufacture often involved mineral-rich colourants, sometimes in combination with crystalline opacifiers, to produce coloured, opaque glass used not for its transparency but rather for its colourful appearance. The precise nature of colourants, opacifiers as well as other (trace) elements in glass has, in a number of cases, been found to be highly specific for both the particular production process employed, including raw materials, and sometimes its provenance [1]. Determining the co-location of different elements in small particulate inclusions in glass can give further crucial information on provenance and on the fabrication technology employed when solely detecting the presence of opacifiers and other (trace) elements is not sufficient. ToF-SIMS is uniquely capable of detecting elements across the periodic table with often very high sensitivity and specificity, coupled with high lateral and depth resolution. 2. Experimental All measurements were carried out in a ToF-SIMS IV instrument (ION-TOF GmbH, Mu ¨nster, Germany) using a pulsed gallium primary ion beam with an energy of 25 kV. Samples were embedded in epoxy resin and polished with diamond paste. Scanning electron microscopy (SEM) was employed to locate inclusions of appropriate size for SIMS analysis. Prior to SIMS analysis the surface area under investigation was sputter-cleaned in the SIMS instrument. Pulsed low energy electrons (20 eV) were used to negate any charging effects due to the primary ion beam. High spatial resolution (ca. 300 nm spotsize, unit mass resolution) and high mass resolution (ca. 5 mm spotsize, mass resolution >6000) data were acquired from each analysed area to aid elemental www.elsevier.com/locate/apsusc Applied Surface Science 252 (2006) 7124–7127 * Corresponding author at: Boots Science Building, School of Pharmacy, University of Nottingham, University Park, Nottingham NG7 2RD, UK. E-mail address: frank.rutten@nottingham.ac.uk (F.J.M. Rutten). 0169-4332/$ – see front matter # 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2006.02.273