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Recent studies have shown that the geothermal systems in Tibet are rich in rare metal elements such as lithium (Li), boron (B), rubidium (Rb), and cesium (Cs). However, the understanding of the origin of Cs-rich geyserite formed by hot springs remains unclear. In this study, a detailed petrological, elemental geochemical, and strontium–neodymium (Sr–Nd) isotopic investigation on Cs-rich geyserite in the Chabu region revealed that opal was the main mineral component of Chabu geyserite; here, some samples were rich in terrigenous clastic material, and well-developed diatom fossils were also present. Chabu geyserite had high contents of SiO₂ (78.95%–94.72%) and Al₂O₃ (3.02%–8.14%) and low contents of Fe₂O₃ (0.21%–1.94%), TiO₂ (0.01%–0.20%), MnO (0.01%–0.15%); additionally, the Fe/Ti ratio, the Al/(Al + Fe) ratio, and the Al/(Al + Fe + Mn) ratio showed large variations. These results indicated different degrees of participation by the terrigenous materials, hydrothermal deposition, and biogenic processes. Chabu geyserite was depleted in transition metal elements (e.g., Sc, V, and Cr) and high field strength elements (e.g., Nb, Zr, and Hf), relatively enriched in large-ion lithophile elements (e.g., Li, Rb, Sr, and Ba), and strongly enriched in Cs, (by up to 100 times the Cs content in the upper crust); in addition, it had low V/Y (1.30–2.00) and U/Th ratios. Chabu geyserite exhibited a right-dipping rare earth element (REE) distribution pattern and had significant negative Eu anomalies (0.26–0.72) and no or weak positive Ce anomalies (0.97–1.36). These results further indicated the influence of terrigenous clastic materials and nonhydrothermal sedimentation factors. The Sr–Nd isotopic composition of Chabu geyserite was significantly different from that of the mantle, with relatively high ⁸⁷Sr/⁸⁶Sr ratios (0.7070–0.7076) and low ¹⁴³Nd/¹⁴⁴Nd ratios (0.512223–0.512314). These ratios were similar to those of the crust. Combined with previous studies, the results from this study indicated that Chabu geyserite was a Cs-rich geyserite and was formed in an intracontinental post-collisional orogenic environment, mainly from crustal material, with the participation of biological and hydrothermal processes. Full article

Single pulse, solid-state ²⁹Si nuclear magnetic resonance (NMR) spectroscopy offers an additional method of characterisation of opal-A and opal-CT through spin-lattice (T₁) relaxometry. Opal T₁ relaxation is characterised by stretched exponential (Weibull) function represented by scale (speed of relaxation) and shape (form of the curve) parameters. Relaxation is at least an order of magnitude faster than for silica glass and quartz, with Q₃ (silanol) usually faster than Q₄ (fully substituted silicates). 95% relaxation (Q₄) is achieved for some Australian seam opals after 50 s though other samples of opal-AG may take 4000 s, while some figures for opal-AN are over 10,000 s. Enhancement is probably mostly due to the presence of water/silanol though the presence of paramagnetic metal ions and molecular motion may also contribute. Shape factors for opal-AG (0.5) and opal-AN (0.7) are significantly different, consistent with varying water and silanol environments, possibly reflecting differences in formation conditions. Opal-CT samples show a trend of shape factors from 0.45 to 0.75 correlated to relaxation rate. Peak position, scale and shape parameter, and Q₃ to Q₄ ratios offer further differentiating feature to separate opal-AG and opal-AN from other forms of opaline silica. T₁ relaxation measurement may have a role for provenance verification. In addition, definitively determined Q₃/Q₄ ratios are in the range 0.1 to 0.4 for opal-AG but considerably lower for opal-AN and opal-CT. Full article

An extensive infrared (IR) spectroscopy study using transmission, specular and diffuse reflectance, and attenuated total reflection (ATR) was undertaken to characterise opal-AG, opal-AN (hyalite), opal-CT and opal-C, focussing on the Si-O fingerprint region (200–1600 cm⁻¹). We show that IR spectroscopy is a viable alternative to X-ray powder diffraction (XRD) as a primary means of classification of opals even when minor levels of impurities are present. Variable angle specular reflectance spectroscopy shows that the three major IR bands of opal are split into transverse optical (TO) and longitudinal optical (LO) components. Previously observed variability in powder ATR is probably linked to the very high refractive index of opals at infrared wavelengths, rather than heterogeneity or particle size effects. An alternative use of ATR using unpowdered samples provides a potential means of non-destructive delineation of play of colour opals into opal-AG or opal-CT gems. We find that there are no special structural features in the infrared spectrum that differentiate opal from silica glasses. Evidence is presented that suggests silanol environments may be responsible for the structural differences between opal-AG, opal-AN and other forms of opaline silica. Complementary studies with Raman spectroscopy, XRD and scanning electron microscopy (SEM) provide evidence of structural trends within the opal-CT type. Full article