Mineralogy and Petrology (2003) 78: 243–253 DOI 10.1007/s00710-002-0227-y Cathodoluminescence of synthetic and natural calcite: the effects of manganese and iron on orange emission S. Cazenave, R. Chapoulie, and G. Villeneuve CRP2A (Centre of Physics for Archaeology), CNRS – UMR 5060 IRAMAT, Bordeaux 3 University, France Received February 19, 2002; revised version accepted October 22, 2002 Published online March 10, 2003; # Springer-Verlag 2003 Editorial handling: J.-P. Eissen Summary The orange cathodoluminescence (CL) of calcite is known to be due to the presence of Mn 2 þ cations. It has been demonstrated here using CL and electron paramagnetic resonance (EPR) crossed analysis from synthetic calcite that neither Fe 2 þ nor Fe 3 þ ions influence this luminescence emission. More complex natural calcium carbonates have been investigated to check whether or not this conclusion can be applied to them. For this purpose, different white marbles from Greek quarries were analysed with CL. The data are completed with neutron activation analysis (NAA) for manganese and iron contents. Again it is shown that only manganese plays a role in the orange CL of these white marbles. This result provides an important clue in the wide field of provenance determination of calcium carbonate used in ancient art. Introduction The aim of this study is to compare the results obtained with cathodoluminescence (CL) on calcite synthesized in our laboratory (CRP2A, Bordeaux, France) with geological materials like marble, where calcite is the only important mineral. This application follows upon an evaluating experimental work about the relative role of Mn 2 þ , Fe 2 þ and Fe 3 þ for the CL behaviour of calcite. The luminescence properties of calcite have been known since the 1950’s (Medlin, 1959) and they have been used in geosciences ever since (Pagel et al., 2000; G€ otze, 2000), often in combination with other techniques such as SEM- EDX, microprobe-WDX, SIMS, PIXE, etc. (Habermann et al., 2000). Luminescent centres and non-luminescent centres have been suggested among which manganese