Unusual luminescence of quartz from La Sassa, Tuscany: Insights on the crystal and defect nanostructure of quartz

Quartz from La Sassa (Tuscany, Italy) presents a unique luminescence related to intrinsic and extrinsic defects in the crystal lattice due to the growth mechanisms in hydrothermal conditions. The bright fluorescence under the UV lamp was apparent to collectors since the early 1970s, and it entered the literature as a reference case of yellow-luminescent quartz. Early reports present the history of the discovery, the geological context, and preliminary luminescence measurements of the quartz nodules, suggesting various activators as potentially responsible of the peculiar luminescence effects: uranyl groups (UO22+), rare earths (Tb3+, Eu3+, Dy3+, Sm3+, Ce3+) and polycyclic aromatic compounds (PAH). Here, we report a full investigation of the La Sassa material, by a multi-analytical approach encompassing cathodoluminescence optical microscopy (OM-CL), laser-induced fluorescence (LIF), wavelength resolved thermally stimulated luminescence (WR-TSL), trace elements analysis by mass spectrometry (ICP-MS) and Raman spectroscopy (RS). The results provide a significant step forward in the interpretation of the luminescence mechanisms: the main luminescent centres are identified as alkali-compensated (mainly Li+ and Na+, K+ and H+) aluminum [AlO4 /M+ ]0 centres substituting for Si, where the recombination of a self-trapped exciton (STE) or an electron at a nonbridging oxygen hole centre (NBOHC) are active.