Oxy-dravite, ideally Na(Al2Mg)(Al5Mg)(Si6O18)(BO3)3(OH)3(O), was found in a composition near its ideal end-member at the Beluga occurrence, Nunavut territory, Canada. It occurs in retrograde albite–muscovite–corundum–calcite domains in a calc-silicate rock. This uncommon oxy-dravite occurs as dark brown, equant to short-prismatic, idiomorphic crystals with vitreous lustre and up to ca. 4 × 3 cm in size. The oxy-dravite is optically uniaxial (–), with ω = 1.6453(5) and ɛ = 1.6074(18); its calculated density is 3.069 g.cm–3 with a compatibility index of 0.016. The Beluga oxy-dravite has trigonal symmetry, space group R3m with a = 15.9121(2) Å, c = 7.1788(10) Å, V = 1574.12(5) Å3 and Z = 3. The crystal structure was refined to R1 = 1.45 using 1613 unique reflections. The empirical crystal-chemical formula is X(Na0.88Ca0.08□0.03K0.01)Y(Al1.49Mg1.31Fe0.15Ti0.04Zn0.01)Z(Al5.42Mg0.58)T(Si5.84Al0.16O18)B(BO3)3V(OH2.95O0.05)W(O0.84OH0.01F0.15).

Oxy-dravite in nature commonly occurs in a solid solution with foitite, schorl and oxy-schorl. At the Beluga occurrence, its minor contents of Al, vacancy [□], and Ca are most likely compensated by (□Al)(NaR2+)–1 and (CaMg)(NaAl)–1 exchanges of the oxy-magnesio-foitite and magnesio-lucchesiite components. The Beluga occurrence of oxy-dravite is characterised by an Mg-rich environment related to a metamorphic overprint of the original sedimentary sequence. This sequence of marine dolomitic argillaceous marl was influenced by (B,Cl)-rich fluids, probably proximally-derived from mineral breakdown reactions in the calc-silicate during the retrograde stage of metamorphism. The locality is a rare example of a tourmaline + corundum assemblage.

Two tourmaline samples occurring in quartz veinlets, which cross-cut an amphibolite body at the Budniki camp near the Kowary town in the south-west part of the Karkonosze Mountains, SW Poland, were studied through microprobe and single crystal X-ray diffraction. Samples were extracted from core and rim regions of crystals with concentric zoning. Chemical and structural data revealed that the core tourmaline is characterised by a dravite–oxy-dravite composition, with the formula: X(Na0.82Ca0.07K0.01Sr0.01□0.09)Σ1Y(Mg1.73Fe2+0.81Fe3+0.41Ti0.04V0.01)Σ3Z(Al5.85Fe3+0.15)Σ6(TSi6O18)(BO3)3(OH)3W(OH0.50O0.50)Σ1 and unit cell parameters a = 15.97377(14) Å and c = 7.22644(7) Å. The rim part of the crystals has a magnesio-lucchesiite composition, described by the formula: X(Ca0.49Na0.41K0.04Sr0.02□0.04)Σ1Y(Mg1.87Fe2+0.95Ti0.15Fe3+0.02V0.02)Σ3Z(Al5.49Fe3+0.51)Σ6(BO3)3(TSi6O18)(OH)3W(O0.81F0.18OH0.01)Σ1 with unit cell parameters a = 15.9863(3) Å and c = 7.22426(15) Å. Both tourmalines show similar refined populations at the Y and Z sites: Y[(Fe2+0.810Mg0.680)Σ1.490(Al1.044Fe3+0.413V0.009)Σ1.465Ti0.045]Σ3Z(Al4.806Mg1.042Fe3+0.152)Σ6 (dravite–oxy-dravite), and Y[(Fe2+0.945Mg0.750)Σ1.695(Al0.737Fe3+0.404V0.018)Σ1.159Ti0.146]Σ3Z(Al4.749Mg1.115Fe3+0.137)Σ6 (magnesio-lucchesiite), with a comparable Mg/(Mg + Fe) ratio of ~0.54–0.56, oxidation of Fe expressed as Fe3+/Fetotal ratio ~0.36–0.41, and trace components such as Ti, Sr, V, Cr, Ni and Co. The geological history of the eastern Karkonosze region in the Kowary vicinity indicates that both tourmalines crystallised from B-bearing metamorphic fluids mobilised by Variscan prograde metamorphism from the protoliths of the Velká Upá mica schists that host the Budniki amphibolite. The fluids migrated into the tectonised amphibolite enriched in Ti, V, Cr, Ni and Co, and mineralised the fractures within it through deposition of soluble species in the form of quartz–tourmaline veinlets. Magnesio-lucchesiite crystallised in an early retrogression stage, probably from Ca- and F-bearing fluids secondary enriched in B by the dissolution of dravite–oxy-dravite. The Budniki camp is, in addition to the type and co-type magnesio-lucchesiite localities, the third documented occurrence of the species worldwide.

A single-crystal neutron diffraction study of oxy-dravite from Osarara (Narok district, Kenya) was performed. Intensity data were collected in Laue geometry at 10 K and anisotropic-structure refinement was undertaken. For the first time, two independent H sites were refined unambiguously for a mineral belonging to the tourmaline supergroup and located at 0.26, 0.13, 0.38 (labelled as H3, site occupancy ∼98%) and at 0, 0, 0.9 (labelled as H1, site occupancy ∼25%). The H-bonding scheme can thus be defined as follows: (1) the O at the O3 site acts as a ‘donor’ and the O at the O5 site as ‘acceptor’, the refined O3–H3 bond distance is 0.972(2) Å (and 0.9946 Å corrected for “riding motion”), H3⋯O5 = 2.263(2) Å, O3⋯O5 = 3.179(1) Å and O3–H3⋯O5 = 156.6(1)°; (2) the oxygen at the O1 site acts as a ‘donor’ and the O atoms at O4 and O5 as ‘acceptors’, the refined O1–H1 bond distance is 0.958(8) Å (and 0.9833 Å corrected for “riding motion”), H1⋯O4 = 2.858(6) Å, O1⋯O4 = 3.378(1) Å and O1–H1⋯O4 = 115.12(1)°, whereas H1⋯O5 = 2.886(6) Å, O1⋯O5 = 3.444(1) Å and O1–H1⋯O5 = 118.23(1)°. A further test refinement was performed with the H1 site out of the three-fold axis (at 0.02, 0.01, 0.90); this leads to O1–H1 = 0.995(8) Å (and 1.0112 Å corrected for “riding motion”), H1⋯O4 = 2.747(6) Å and O1–H1⋯O4 = 121.7(4)°, whereas H1⋯O5 = 2.654(9) Å and O1–H1⋯O5 = 136.5(6)°. Bond-valence analysis shows that the H-bonding strength involving O3 is stronger than that involving O1: ∼0.11 and <0.05 valence units, respectively.

The refined angle between the O3–H3 vector and [0001] is 3.40(9)°. Such a small angle is in line with a pleochroic scheme for the OH-stretching absorption bands measured by infrared spectroscopy.

Yellowish dravitic tourmaline (dominated by the oxy-dravite component) associated with secondary fluor-dravite/fluor-schorl and dravite/schorl tourmalines was found in a quartz vein cropping out in the eastern part of the Karkonosze Mountains range, SW Poland. The crystal structure of this tourmaline was refined to an R1 value of 1.85% based on single-crystal data, and the chemical composition was determined by electron-microprobe analysis. The tourmaline, a representative of the alkali-tourmaline group, has the structural formula: (Na0.75Ca0.12□0.13)Σ1(Mg1.93Al0.95Ti0.06${\rm Fe}_{{\rm 0}{\rm. 04}}^{{\rm 2 +}} $ V0.01)Σ3(Al5.38Mg0.62)Σ6B3Si6O27(OH)3(O0.46OH0.33F0.21)Σ1, and is characterized by an extremely high Mg/(Mg + Fe) ratio of 0.97–0.99, the WO2– content that reaches 0.59 apfu resulting in a local predominance of the oxy-dravitic component and Mg–Al disorder on the octahedral Y and Z sites of the order of 0.64 apfu. This disordering results in an increasing <Z–O> distance with ~1.925 Å, and unit-cell parameters a = 15.916(1) Å and c = 7.180(1) Å. The tourmaline formed during Variscan prograde metamorphism under the influence of a released (H2O,B,F)-bearing fluid. The fluid mobilized the most soluble components of partly altered silicic volcaniclastic material of the Late Cambrian to Early Ordovician bimodal volcanism to become the protolith for adjacent quartzo-feldspathic schists and amphibolites, and propagated them into the surrounding granitic gneisses of the Kowary unit in the eastern metamorphic cover of the Karkonosze granite.