Application of statistical analyses for lapis lazuli stone provenance determination by XRL and XRF

Lapis lazuli use stretches back more than 6500 years; ancient civilizations of Mesopotamia, Egypt, China, Greece, and Rome treasured and prized it. Afghanistan has been the oldest source for this stone, while Chile, Canada, Russia and a few other countries have been reported as sources for raw material in more recent times; the rarity of historical mines surely represents a positive aspect for the provenance clue of artefacts. Lapis lazuli is a rock consisting mainly of lazurite, to which it owes the blue colour, calcite and pyrite. Other constituents may be present, related to the different mines. In the present work, we apply the principles of Radio-luminescence (RL) exploiting as radiation source the X-ray tube of a portable commercial X-Ray Fluorescence spectrometer; in this way, X-Ray Fluorescence spectra (XRF) can be simultaneously acquired to have a larger set of data. To highlight the instrumental experimental differences, we refer to the portable set up as X-Ray Luminescence (XRL), as suggested by recent literature. We thus looked for the possibility of applying a wieldy, low cost and non-destructive method that could fit also to precious objects, based on the join use of XRF and XRL. We performed analyses on raw lapis lazuli stones from five different provenances, both historical and modern, and on four sets of unknown origin carved polished stones, to test our methods on real artefacts. We focalised on a limited number of samples to concentrate on the statistical treatment of spectra obtained, so to get a synergic response of the two applied techniques. We were able to obtain a clear distinction for the different classified provenances and could speculate those of unknown samples.