Alloy characterization of a 7th Century BC archeological bronze vase — Overcoming patina constraints using Monte Carlo simulations.

In this work we evaluate the composition of a bronze alloy using X-ray fluorescence spectrometry (XRF) and Monte Carlo (MC) simulations. For this purpose, a 7th Century BC archeological vase from the SW Iberian Peninsula, displaying a well formed corrosion patina was analyzed by means of a portable X-ray fluorescence spectrometer. Realistic MC simulations of the experimental setup were performed with the XRMC code package which is based on an intensive use of variance-reduction techniques and uses XRAYLIB a constantly updated X-ray library of atomic data. A single layer model was applied for simulating XRF of polished/pristine bronze whereas a two-or-three-layer model was developed for bronze covered respectively by a corrosion patina alone or coupled with a superficial soil derived crust. These simulations took into account corrosion (cerussite (PbCO 3 ), cuprite (Cu 2 O), malachite (Cu 2 CO 3 (OH) 2 ), litharge (PbO)) and soil derived products (goethite (FeO(OH)) and quartz (SiO 2 )) identified by means of X-ray diffraction and Raman micro analytical techniques. Results confirm previous research indicating that the XRF/Monte Carlo protocol is well suited when a two-layered model is considered, whereas in areas where the patina + soil derived products' crust is too thick, X-rays from the alloy substrate are not able to exit the sample. Quantitative results based on MC simulations indicate that the vase is made of a lead–bronze alloy: Mn (0.2%), Fe (1.0%), Cu (81.8%), As (0.5%), Ag (0.6%), Sn (8.0%) and Pb (8.0%). [ABSTRACT FROM AUTHOR]