Portable X-Ray Fluorescence as a Proxy for Aerinite in Pigments of Medieval Alto Aragón Cultural Heritage

Aerinite is a rare blue aluminosilicate mineral whose identification as a pigment in Pyrenean medieval artworks typically requires invasive microsampling. This study evaluates portable X-ray fluorescence spectroscopy (pXRF) as a noninvasive screening tool for aerinite in Alto Aragón (Spain) cultural heritage. Elemental compositions of aerinite and lapis lazuli references, ceramics, polychromed capitals, and thirteenth- to fifteenth-century painted panels were measured with a Niton XL3t GOLDD+ spectrometer. Data were analyzed using log-ratio linear discriminant analysis (LDA), with silicon as an internal normalizer. Aerinite references showed Cu and Co levels below instrumental detection limits, along with Fe (6.99 ± 1.04 wt%), Al (4.91 ± 1.38 wt%), and Si (15.95 ± 1.60 wt%). High-confidence aerinite classifications were obtained for Cu-free and Co-free blue pigments in the Barbastro Chrismon, the Buira altar frontal, and other panels. Extension of the protocol to green pigments revealed that two samples—from the Saint Anthony Abbot panel and Portaspana retable—were also classified as aerinite, providing the analytical evidence for “verde de Juseu” as a naturally occurring greenish aerinite variety. Despite known pXRF limitations, this technique effectively screens candidate aerinite-containing passages for subsequent microanalytical confirmation.