In recent years, some sapphires were found to fade in sunlight and to increase their color after UV irradiation. This unstable color phenomenon is attributed to the photochromism of corundum. The photochromic effect seriously affects the grading and evaluation of sapphires, although its mechanism is still uncertain. Here, we performed a set of photochromic experiments on sapphire specimens using a 254 nm shortwave UV light source and a D65 light source (which simulates sunlight) to generate different color states exhibiting characteristic absorption, emission, and excitation spectra. We observed that, for different color states, variation in the intensity of the absorption band at ~460 nm was consistent with that of orange fluorescence at 500–800 nm. This observation indicates a relationship between color instability and orange fluorescence. Peaks in excitation spectra at 320, 420, 490, 560, and 637 nm provide insight into the source(s) of excited orange fluorescence, which are related to different types of F-centers and Mg-trapped holes. We propose an explanation for the photochromic phenomenon: the color of photochromic yellow sapphire is the result of a variety of defects that release orange fluorescence simultaneously. Further, we hypothesize that the mechanism of photochromism in yellow sapphires is linked to electron transfer between F-centers and Mg-trapped holes.@en

Smectites affecting water and soil exchangeable cations, especially potassium and ammonium related to plants, are common swelling clay minerals in sediments and paleosols that can record paleoenvironmental and paleoclimatic information. Paleoenvironmental and paleoclimatic interpretations are potentially ambiguous, because smectite minerals may have either detrital or pedogenic origins. This study analyzes smectites in Lower Eocene paleosols of the Qaidam Basin, China, with the goal of determining their origin and paleoclimatic significance. Twelve smectite-rich vertisol samples were analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), inductively coupled plasma-mass spectrometry (ICP-MS), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC) in the Dahonggou (DHG) section of the Lulehe Formation. The samples from DHG section contained predominant dioctahedral smectites (60–65%) in the <2 μm clay fractions. Minor dioctahedral illites, dioctahedral interstratified illite-smectite (I-Sm), kaolinite, and traces of dioctahedral chlorites and palygorskites were present. The chemical data and FTIR spectra revealed both tetrahedral substitutions (i.e., Al for Si) and octahedral substitutions (i.e., Mg and minor Fe for Al) in the dioctahedral smectites. Montmorillonite comprised the dominance of the fine-clay fractions (< 0.2 μm) with minor contributions of beidellite, as determined by the Greene-Kelly test (GK-test), geochemical and FTIR analyses. SEM observations revealed two morphological types of dioctahedral smectites, the less abundant one with typical ‘honeycomb’ structure, interpreted as neoformed, and the other occurring as thin, well-defined plates and irregular masses considered to be detrital. DSC revealed two dehydroxylation temperatures (500–550 °C and 600–700 °C), indicating the presence of trans-vacant (tv) and cis-vacant (cv) layers, respectively. The cv layers were attributed to montmorillonite originating as catchment-delivered detritus, as the study Lulehe Formation exhibited no evidence of volcanic ash layers or diagenesis that would have promoted formation of montmorillonite with high dehydroxylation temperatures. The tv layers represented pedogenic beidellite formed via solution crystallization in a floodplain pedogenic environment. The accumulation of abundant inherited montmorillonite and neoformed beidellite in paleosols of the Lulehe Formation was probably promoted by a relatively warm climate with alternating wet-dry seasons during the Early Eocene. Admixture of detrital montmorillonite makes paleoclimatic reconstructions based on bulk-smectites concentrations and isotopic compositions unreliable, showing that integrated clay mineralogical analyses of the type undertaken in this study are necessary to identify the provenance and paleoclimatic significance of smectites in sediments.@en