This article reviews blue shortwave-excited luminescence (BSL) in natural minerals and synthetic materials. It also describes in detail the emission of seven minerals and gems displaying BSL, as well as three references in which BSL is caused by titanate groups (TiO₆): benitoite, Ti-doped synthetic sapphire and spinel. Emission (under 254 nm shortwave excitation) and excitation spectra are provided, and fluorescence decay times are measured. It is proposed that BSL in beryl (morganite), dumortierite, hydrozincite, pezzotaite, tourmaline (elbaite), some silicates glasses, and synthetic opals is due to titanate groups present at a concentration of 20 ppmw Ti or above. They all share a broad emission with a maximum between 420 and 480 nm (2.95 to 2.58 eV) (thus perceived as blue), and an excitation spectrum peaking in the short-wave range, between 230 and 290 nm (5.39 to 4.27 eV). Furthermore, their luminescence decay time is about 20 microseconds (from 2 to 40). These three parameters are consistent with a titanate emission, and to our knowledge, no other activator.

Iron-titanium (Fe-Ti) charge transfer is mentioned in numerous articles as the source of the coloration of many natural minerals and some manufactured materials, but no global review of this phenomenon has been provided so far. Iron and titanium are ubiquitous in nature and are often found in the same material as Fe2+ and Fe3+, and Ti4+ (more rarely Ti3+). When Fe and Ti ions are in close geometric proximity in an oxide or (alumino)silicate structure, charge transfer can occur between the two ions, even though their concentration might be below 100 ppm. This results in a variety of absorption features that contribute to the color of minerals. A debate remains on the exact nature of Fe/Ti electronic transition, i.e., Fe2+ + Ti4+ → Fe3+ + Ti3+ or the reverse, but solving this issue is not within the scope of the present work. Ascertaining a metal-metal charge transfer is often not straightforward. This review compiles existing knowledge on Fe-Ti charge transfer in both crystalline and amorphous materials and identifies several key characteristics in more than 40 different materials. A charge transfer is associated with broad, intense, optical absorption bands that decrease in intensity at elevated temperatures. It is also strongly pleochroic in non-isotropic materials. Until now, Fe-Ti charge transfer transitions have been primarily described in the 2.25 to 3.1 eV range, corresponding to yellow to orange to brown colors, with notable exceptions such as blue sapphire or kyanite, and green andalusite. This review suggests that Fe-Ti charge transfer can occur across the entire visible spectrum, and the position of the absorption band correlates with the Fe-Ti interatomic distance. This correlation highlights the presence of multiple crystallographic sites for both Fe and Ti in many oxides, leading to multiple Fe-Ti bands within these materials (e.g., sapphire, ilmenite, pseudobrookite). Finally, the use of metal-metal distances is suggested to differentiate this heteronuclear Fe-Ti charge transfer from the common homonuclear charge transfer Fe2+-Fe3+.

Fifteen opal samples of gem quality from the Spencer Opal Mines in Idaho (USA) were examined. These opals display play-of-colour, with three of them having a pink body colour. The analysis was conducted using standard gemmological tools, along with non-destructive spectroscopic, chemical, and imaging methods. All samples were identified as opal-A, with their play-of-colour resulting from a regular stacking of hydrated silica spheres. However, at times, the spheres are large to allow diffraction. Opal-A are only occasionally found in nature as gems. Inclusion observed in the studied samples included alunite (KAl₃(SO₄)₂(OH)₆), anhydrite (CaSO₄), and iron-rich spherules (hematite). The pink body colour in the studied specimens is caused by the scattering of light from reddish dendrites. The samples show significant stratification, with fluorescence ranging from green to blue to orange, the latter of which represents a new phenomenon in opals not associated with quinones. Additionally, the orange fluorescence is accompanied by emissions from Sm²⁺ in anhydrite inclusions.