Olenitic tourmaline with high amounts of tetrahedral B (up to 2.53 [4]B pfu) has been synthesized in a piston-cylinder press at 4.0 GPa, 700 °C, and a run duration of 9 days. Crystals are large enough (up to 30 × 150 μm) to allow for reliable and spatially resolved quantification of B by electron microprobe analysis (EMPA), single-crystal X-ray diffraction, and polarized single-crystal Raman spectroscopy. Tourmalines with radial acicular habit are zoned in [4]B-concentration [core: 2.53(25) [4]B pfu; rim: 1.43(15) [4]B pfu], whereas columnar crystals are chemically homogeneous [1.18(15) [4]B pfu]. An amount of 1.4(1) [4]B pfu was found in the columnar tourmaline by single-crystal structure refinement (SREF) (R = 1.94%). The EMPA identify [T]Si−1[V,W]O−1[T]B1[V,W](OH)1 as the main and [X]−1[T]Si−1[X]Na1[T]B1 as minor exchange vectors for [4]B-incorporation, which is supported by the SREF. Due to the restricted and well-defined variations in chemistry, Raman bands in the OH-stretching region (3000–3800 cm−1) are unambiguously assigned to a specific cation arrangement. We found the sum of the relative integrated intensity (Irel) of two low-frequency bands at 3284–3301 cm−1 (ν1) and 3367–3390 cm−1 (ν2) to positively correlate with the [4]B concentrations: [4]B [pfu] = 0.03(1) × [Irel (ν1) + Irel (ν2)]. Hence, those bands correspond to configurations with mixed Si/B occupancy at the T site. Our semi-quantitative correlation also holds for well-characterized natural [4]B-bearing tourmaline from the Koralpe, Austria. This work shows the potential for Raman spectroscopy as a non-destructive method for the chemical classification of (precious) natural tourmaline, and as a tool to rapidly characterize chemical zonation of tourmalines in thin section.

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