Micro‐Raman imaging and spectroscopy has become an established technique for the characterization of biogenic hydroxyapatite as, for example, the primary constituent of human teeth. However, few studies have yet gone beyond a qualitative analysis of the Raman response providing only limited insight into spatial heterogeneity of composition, structure, and degree of crystallinity. Here, we show how correlative electron microprobe and extended hyperspectral Raman imaging with high spatial and spectral resolution, with peak position and linewidth analysis, and from the μm to mm scale, provides insight into structural characteristics in dentin and enamel. From comparison of healthy and hypoplastic teeth as a representative tooth disease example, we determine variations in degree of crystallinity, both locally across the dentin–enamel junction, and with distinct long‐range spatial variations. We identify a correlation of spectral peak position and linewidth as a measure of crystal lattice disorder across tubules, dentin, dentin–enamel junction, and enamel. This correlative Raman imaging and analysis approach may help to provide a better understanding of apatite geochemistry and biomineralization.

A previously undescribed small lenticular (~5 × 5 × 5 m) pegmatite, located near Wellington Lake in the NW part of the 1.08 Ga ‘A-type’ (anorogenic) ferroan Pikes Peak granite batholith, ~15 km SW of the South Platte pegmatite district in central Colorado, is concentrically zoned around a mostly monomineralic quartz core with interconnected miarolitic cavities. Major constituents of the Wellington Lake pegmatite are quartz, perthitic microcline, albite (variety cleavelandite), hematite, and biotite. Accessory minerals include fluocerite, bastnäsite, columbite, zircon (var. ‘cyrtolite’), thorite, and secondary U phases. Fluorite is conspicuously absent, although it is a common phase in the South Platte district NYF-type pegmatites, which are rich in niobium (Nb), yttrium (Y), fluorine (F), and heavy rare-earth elements (HREE). Notable for the Wellington Lake pegmatite are a small quantity of well-developed tabular crystals of fluocerite that reach up to 4 cm in diameter, with sub-mm epitaxial bastnäsite overgrowths, suggesting formation from F- and CO2-bearing solutions rich in light rare-earth elements (LREE), with decreasing a(F-)/a(CO32-) during the last crystallization phase. An Nd-isotope value of εNd1.08Ga = -1.6 for the fluocerite is within the range of εNd1.08Ga = -0.2 to -2.7 of the host coarse-grained, pink K-series Pikes Peak Granite (PPG), indicating that REE and other pegmatite constituents derived from the parental PPG magma. A calculation of total pegmatite composition based on whole-rock chemistry and volume estimates of the different pegmatite zones reveals an overall composition similar to the PPG with respect to Si, Al, Na, and K. Yet the pegmatite is depleted in Fe, Mg, Ca, Ti, Mn, and P, the high-field-strength elements (HFSE; Zr, Hf, Nb, Y, Th), and, most significantly, total REE compared to the PPG. Despite containing the LREE minerals fluocerite and bastnäsite, the lack of a net overall REE enrichment of the pegmatite compared to the PPG reflects the large amount of REE-poor silicate minerals forming the wall, intermediate, and core zones of the pegmatite. The calculated total pegmatite composition suggests that the pegmatite formed by the separation from the PPG magma of an F-poor H2O-saturated silicate melt depleted in REE and HFSE compared to the F-rich melts, which formed the NYF-type HREE-rich (LaN/YbN < 1) pegmatites in the South Platte district. Homogenization temperatures of < 500°C for possibly primary fluid inclusions in large quartz crystals from the core of the Wellington Lake pegmatite are consistent with recent models of pegmatite petrogenesis leading to nucleation controlled mega-crystal growth resulting from supercooling.

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Beryl from Xuebaoding, Sichuan Province, western China is known for its unusual tabular habit and W–Sn–Be paragenesis in a greisen-type deposit. The crystals are typically colourless transparent to pale blue, often with screw dislocations of hexagonal symmetry on the (0001) crystal faces. Combining electron microprobe analyses and laser ablation inductively coupled plasma mass spectrometry with single-crystal X-ray diffraction (XRD), correlated with Raman and micro-infrared (IR) spectroscopy and imaging, the crystal chemical characteristics are determined. The contents of Na+ (0.24–0.38 atoms per formula unit (apfu)) and Li+ up to 0.38 apfu are at the high end compared to beryl from other localities worldwide. Li+ substitution for Be2+ on the tetrahedral (T2) site is predominantly charge balanced by Na+ on the smaller channel (C2) site, with Na+ ranging from 91.5% to 99.7% (apfu) of the sum of all other alkali elements. Cs+ and minor Rb+ and K+ primarily charge balance the minor M2+ substitution for Al3+ at the A site; all iron at the A site is suggested to be trivalent. The a axis ranges from 9.2161(2) to 9.2171(4) Å, with unit-cell volume from 678.03(3) to 678.48(7) Å3. The c/a ratio of 1.0002–1.0005 is characteristic for T2-type beryl with unit-cell parameters controlled primarily by Be2+ substitution. Transmission micro-IR vibrational spectroscopy and imaging identifies coordination of one or two water molecules to Na+ (type IIs and type IId, respectively) as well as alkali free water (type I). Based on IR absorption cross section and XRD a C1 site water content of 0.4–0.5 apfu is derived, i.e. close to 50% site occupancy. Secondary crystal phases with a decrease in Fe and Mg, yet increase in Na, suggest early crystallisation of aquamarine, with goshenite being late. With similar crystal chemistry to beryl of columnar habit from other localities worldwide, the tabular habit of Xuebaoding beryl seems to be unrelated to chemical composition and alkali content.