Samples of manganese-rich rock containing two compositional varieties of tokyoite in association with noélbensonite were retrieved from a drill core obtained from the Postmasburg area in the Northern Cape Province of South Africa. The samples consist of fine-grained braunite, hematite, and hausmannite. Within this material abundant vugs are observed that are filled with witherite, baryte, and barytocalcite. In addition, As-rich tokyoite, tokyoite, and noélbensonite occur in the center of the vugs, in fine aggregates 0.1 to 1 mm in size. Individual As-rich tokyoite grains are typically 20–200 μm in size. The outer walls of the vugs are lined with microcrystalline K-feldspar, witherite, and/or sérandite. Textural evidence of the Ba-rich mineral phases in association with As-rich tokyoite suggest an epigenetic mode of formation of the observed assemblages, caused by V- and As-bearing alkali-rich fluids interacting with pre-existing Mn-rich minerals.

Electron microprobe analysis (EMPA), electron backscatter diffraction analysis (EBSD), and Raman spectroscopy show that the As-rich tokyoite is a mineral belonging to the brackebuschite mineral group. Its measured mineral composition corresponds to the formula (Ba1.92Sr0.05Pb0.03)∑2.00(Mn3+0.98Fe3+0.02)∑1.00[(As1.050V0.950)∑2.00O8)](OH). Electron backscatter diffraction analysis results point to a monoclinic, P21/m space group, with cell parameters a 9.121 Å, b 6.142 Å, c 7.838 Å, α = γ = 90°, β = 112°, Z = 2. The structure is therefore similar to gamagarite. Raman spectra of As-rich tokyoite were compared to spectra of arsenbrackebuschite and arsentsumebite, and those of noélbensonite to spectra of hennomartinite and lawsonite. The indexing of Raman peaks in As-rich tokyoite, by similarity with arsentsumebite, suggests a possible ordering of the AsO4 and VO4 tetrahedra. This observation, correlated with mineral chemistry and specifically an As:V ratio of ~1:1, suggest that the As-rich tokyoite may in fact represent a possible new mineral with ordering of As and V at tetrahedral positions, or at least an unknown As analogue of tokyoite.

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