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.

Multicoloured tourmalines from Elba Island, commonly display dark-coloured terminations due to incorporation of Fe, and also occasionally Mn. The mechanisms which led to the availability of these elements in the late-stage residual fluids are not yet completely understood. For this purpose, we investigated a representative tourmaline crystal found naturally in two fragments within a wide miarolitic cavity in the Rosina pegmatite (San Piero in Campo, Elba Island, Italy), and characterised by late-stage dark-coloured overgrowths. Microstructural and paragenetic observations, together with compositional and spectroscopic data (electron microprobe and optical absorption spectroscopy), provide evidence which shows that the formation of the dark-coloured Mn-rich overgrowths are the result of a pocket rupture. This event caused alteration of the cavity-coating spessartine garnet by highly-reactive late-stage cavity fluids by leaching processes, with the subsequent release of Mn to the residual fluids. We argue that the two fragments were originally a single crystal, which underwent natural breakage followed by the simultaneous growth of Mn-rich dark terminations at both breakage surfaces. This conclusion supports the evidence for a pocket rupture event, responsible for both the shattering of the tourmaline crystal and the compositional variation of the cavity-fluids related to the availability of Mn, which was incorporated by the tourmaline crystals. Additionally, a comparison of the dark overgrowths formed at the analogous and the antilogous poles, provides information on tourmaline crystallisation at the two different poles. The antilogous pole is characterised by a higher affinity for Ca, F and Ti, and a selective uptake of Mn2+, even in the presence of a considerable amount of Mn3+ in the system. This uneven uptake of Mn ions resulted in the yellow–orange colouration of the antilogous overgrowth (Mn2+ dependent) rather than the purple-reddish colour of the analogous overgrowths (Mn3+ dependent).

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.

Black tourmalines from seven granitic pegmatites (Golodnaya, Kazennitsa, Mokrusha, Kopi Mora, Zheltyye Yamy, Buzheninov Bor and Ministerskaya) related to the Murzinka pluton, Central Urals, Russia have been investigated using electron microprobe analysis, LA-ICP-MS, Raman and Mössbauer spectroscopy. Pegmatites are hosted by serpentinites and gneisses and are classified as schorl, oxy-schorl, fluor-schorl, dravite, oxy-dravite, foitite, oxy-foitite and darrellhenryite. The possible compositional evolution of tourmalines from the Ural pegmatites is as follows: Mg-rich dravite through to Fe-rich schorl, foitite and oxy-foitite to Fe- and Mn-rich darrellhenryite. The major substitutions in the tourmalines are: (1) Fe2+ ↔ Mg; (2) Al + WO2– ↔ Fe2+ + WOH–; (3) X-site vacancy + Al ↔ Na + Fe2+; (4) Al + WO2– ↔ Mg + WOH–; (5) X-site vacancy + Al ↔ Na + Mg; and (6) Fe ↔ Mn. Statical processing of the trace- and major-element composition distinguished three tourmaline groups: (1) trace Co, Ni, Pb, and major Ca and Mg; (2) uni-, di- and trivalent traces (Li, Zn, Ga) and di- and trivalent majors (Al, Mn); (3) U, Th, Hf, Ta, Nb, Y, In, and Sn which correspond to tri-, tetra-, and pentavalent high-field-strength elements. Mössbauer data shows the Fe3+/Fe2+ ratios in tourmalines from pegmatites hosted by gneisses (0.05–0.18) and serpentinites (0.28–0.65), indicates different oxidising environments. Raman data are consistent with the composition of the tourmalines.

Two tourmaline crystals with a blue growth zone at the analogous pole, respectively from the San Silvestro and the Fucili pegmatites, located in the San Piero in Campo village, Elba Island (Tyrrhenian Sea, Italy), have been described for the first time using compositional and spectroscopic data to define their crystal-chemical aspects and the causes of the colour. Compositional data obtained by electron microprobe analysis indicate that both tourmalines belong to the elbaite–fluor-elbaite series. The upper part of each crystal is characterised by an increased amount of Fe (FeO up to ~1 wt.%) and a Ti content below the detection limit. Optical absorption spectra recorded on the blue zone of both samples show absorption bands caused by spin-allowed d-d transitions in [6]-coordinated Fe2+, and no intervalence charge transfer Fe2+-Ti interactions, indicating that Fe2+ is the only chromophore. Mössbauer analysis of the blue zone of the Fucili sample confirmed the Fe2+ oxidation state, implying that the redox conditions in the crystallisation environment were relatively reducing. The presence of colour changes at the analogous termination during tourmaline crystal growth suggests a change in the composition of the crystallisation environment, probably associated with a partial opening of the system.

Uvite, CaMg3(Al5Mg)(Si6O18)(BO3)3(OH)3(OH), is a new mineral of the tourmaline supergroup. It occurs in the Facciatoia quarry, San Piero in Campo, Elba Island, Italy (42°45′04.55″N, 10°12′50.89″E) at the centre of a narrow (2–3 cm wide) vein composed of aggregates of dark brown to black tourmaline, penetrating (magnesite + dolomite)-rich hydrothermally altered metaserpentinite. Crystals are euhedral and up to 1 cm in size, brown with a vitreous lustre, conchoidal fracture and grey streak. Uvite has a Mohs hardness of ~7½, a calculated density of 3.115 g/cm3 and is uniaxial (–). Uvite has trigonal symmetry, space group R3m, a = 15.9519(10) Å, c = 7.2222(5) Å, V = 1597.3(1) Å3 and Z = 3. The crystal structure was refined to R1 = 1.77% using 1666 unique reflections collected with MoKα X-rays. Crystal-chemical analysis resulted in the empirical crystal-chemical formula $^X ({\rm Ca}_{0.61}{\rm Na}_{{0.35}} \square_{{0.04}})_{\Sigma 1.00}{}^{Y} \left( {{\rm Mg}_{1.50}{\rm Fe}^{2 + }_{0.47} {\rm Al}_{0.71}{\rm Fe}^{3 + }_{0.14} {\rm Ti}_{0.18}} \right)_{\Sigma 3.00}$${}^{Z} \left( {{\rm Al}_{4.54}{\rm Fe}^{3 + }_{0.18} {\rm V}^{3 + }_{0.02} {\rm Mg}_{1.27}} \right)_{\Sigma 6.00}{}^{T}\left[ {{\left( {{\rm Si}_{5.90}{\rm Al}_{0.10}} \right)}_{\Sigma 6.00}{\rm O}_{18}} \right]{\rm } \left( {\rm BO_3} \right)_3^{} {^{\rm O(3)}}\left( {\rm OH} \right)_3{}^{{\rm O}\left( 1 \right)} [\left( {\rm OH} \right)_{0.55}{\rm F}_{0.05}{\rm O}_{0.40}]_{\Sigma 1.00}$

which recast in its ordered form for classification purposes is:

$$\eqalign{& ^{\rm X} ({\rm Ca}_{0.61}{\rm Na}_{0.35}\squ _{0.04})_{\Sigma 1.00}{}^{\rm Y} \left( {{\rm Mg}_{2.35}{\rm Fe}^{2 + }_{0.47} {\rm Ti}_{0.18}} \right)_{\Sigma 3.00} \cr & {}^{\rm Z} \left( {{\rm Al}_{5.25}{\rm Fe}^{3 + }_{0.32} {\rm V}^{3 + }_{0.02} {\rm Mg}_{0.42}} \right)_{\Sigma 6.00}{}^{\rm T} \left[ {{\left( {{\rm Si}_{5.90}{\rm Al}_{0.10}} \right)}_{\Sigma 6.00}{\rm O}_{18}} \right]{\rm }\left( {\rm BO_3} \right)_3{}^{\rm V} \left( {\rm OH} \right)_3{}^{\rm W} [\left( {\rm OH} \right)_{0.55}{\rm F}_{0.05}{\rm O}_{0.40}]_{\Sigma 1.00}}$$

An extensive dataset of major- and trace-element and B-isotope composition related to the compositional variation of the tourmalines from the S-type granite and pegmatite from the Upper Bonai and Gangpur Group granitoids, eastern India, is provided. The Gangpur Schist Belt, consisting of the Upper Bonai and Gangpur Group, lies at the eastern end of the Proterozoic Central Indian Tectonic Zone. An attempt to constrain the source of the boron isotope and describe the magmatic–hydrothermal evolution of the granite–pegmatite system is made. The tourmalines record generally low trace-element concentrations, with the exception of some elements such as Zn, Li, Ga, Mn and Ti. The Zn and Li concentration increases from the tourmalines in the granites to the tourmalines in the pegmatite. Trace-element compositions also vary slightly from the core tourmaline to the rim tourmaline. Tourmalines in granites/pegmatites are mostly Fe-rich schorl, and have S-type B-isotopic signature (δ11B = −10‰ to −12‰). Their chemistries reflect changing salinities of the granitic melts as well as vapour exsolution during progressive crystallization. This study indicates that the tourmalines in the pegmatites crystallized from evolved flux-element-rich (F, B, Li) melt, probably after the crystallization of granite-forming melt.

A green tourmaline sample from the Tzarevskoye uranium–vanadium deposit, close to the Srednyaya Padma deposit, Lake Onega, Karelia Republic, Russia, has been found to be the second world-occurrence of Cr-rich vanadio-oxy-dravite in addition to the Pereval marble quarry, Sludyanka crystalline complex, Lake Baikal, Russia, type-locality. From the crystal-structure refinement and chemical analysis, the following empirical formula is proposed: X(Na0.96K0.02□0.02)Σ1.00Y(V1.34Al0.68Mg0.93Cu2+0.02Zn0.01Ti0.01)Σ3.00Z(Al3.19Cr1.36V0.03Mg1.42)Σ6.00(TSi6O18)(BBO3)3V(OH)3W[O0.60(OH)0.23F0.17]Σ1.00. Together with the data from the literature, a compositional overview of Al–V–Cr–Fe3+-tourmalines is provided by using [6]Al–V–Cr–Fe3+ diagrams for tourmaline classification. These diagrams further simplify the tourmaline nomenclature as they merge the chemical information over the octahedrally-coordinated sites (Y and Z) by removing the issues of uncertainty associated with cation order–disorder across Y and Z. Results show the direct identification of tourmalines by using the chemical data alone.

Tourmaline from the Solnechnoe hydrothermal granitoid-related tin deposit in the Khabarovsk Krai, Russian Far East has been studied with electron microprobe, infrared and Mössbauer spectroscopy. Tourmaline formed in three distinct stages with different types of chemical substitution. Tourmaline from the first unmineralised stage is classified as dravite or schorl, which could be enriched locally in Ca, the X-site vacancy and F. This tourmaline is characterised by the Fe ↔ Mg and X vacancy + Al ↔ Na + Fe substitutions. The second, molybdenum-stage tourmaline, is schorl–dravite and fluor-schorl–fluor-dravite enriched in Ca, and a few compositions belong to the calcic group. The predominant substitution is Ca + Mg ↔ Na + Al. The third, tin-stage tourmaline, is classified as schorl–dravite with some tourmalines being fluor-schorl, oxy-schorl, foitite and magnesio-foitite. The tin-stage tourmaline is characterised by the substitutions Fe2+ ↔ Mg, Altot + O2– ↔ Fe2+ + OH–, and Fe3+ ↔ Altot. An increase of the Fe3+/Fetot value from 3–9% in the molybdenum stage to 12–16% in the tin-stage tourmalines indicates an increase in oxidation potential, which possibly contributed to cassiterite deposition. Comparison of tourmalines from greisen, porphyry and intrusion-related tin deposits worldwide shows they differ in primary chemical substitutions so can be characterised by this mechanism. The Fe3+/Fetot value in tourmaline also appears to be one of the indications for the tin deposit type. The Fe3+/Fetot value increases from <10% in greisen tourmaline through 15% in tourmaline from intrusion-related deposits to 20% in tourmaline from porphyry deposits.

The determination of low boron concentrations in silicate glasses by electron probe microanalysis (EPMA) remains a significant challenge. The internal interferences from the diffraction crystal, i.e. the Mo-B4C large d-spacing layered synthetic microstructure crystal, can be thoroughly diminished by using an optimized differential mode of pulse height analysis (PHA). Although potential high-order spectral interferences from Ca, Fe, and Mn on the BKα peak can be significantly reduced by using an optimized differential mode of PHA, a quantitative calibration of the interferences is required to obtain accurate boron concentrations in silicate glasses that contain these elements. Furthermore, the first-order spectral interference from ClL-lines is so strong that they hinder reliable EPMA of boron concentrations in Cl-bearing silicate glasses. Our tests also indicate that, due to the strongly curved background shape on the high-energy side of BKα, an exponential regression is better than linear regression for estimating the on-peak background intensity based on measured off-peak background intensities. We propose that an optimal analytical setting for low boron concentrations in silicate glasses (≥0.2 wt% B2O3) would best involve a proper boron-rich glass standard, a low accelerating voltage, a high beam current, a large beam size, and a differential mode of PHA.

The nature and mode of origin of quartz-cored tourmalines (QCT) are studied from hydrothermal quartz veins within massive quartz-tourmaline (MQT) rocks at Roche, SW England. The QCT are annular, have blue maximum absorption colour and occur together with tourmalines with brown cores rimmed by blue tourmaline. Where the quartz core is not continuous throughout the length of the QCT crystals, the tourmaline core has brown maximum absorption colour, similar to tourmalines without quartz cores. Both the blue and brown tourmalines are schorl, but are compositionally distinct showing different Fe/(Mg + Ti) ratios and Ca concentrations. Fluid inclusion data indicate quartz precipitation from a moderate salinity (∼20–25 wt.% NaCl eq.) brine which periodically boiled following pressure drops within the vein system. The QCT show rheomorphic and lobate textures on their inner margins indicating selective dissolution of their brown, relative Mg-, Ti- and Ca-rich tourmaline cores and replacement with quartz. This presents a problem in terms of the nature of the fluid responsible for such selective dissolution because tourmaline is generally highly resistant under the normal range of hydrothermal fluid conditions. It is proposed that the relatively high concentrations of Ti, Mg and Ca in the brown tourmaline caused significant lattice strain, which together with an increase in pH, and probably Al, in the boiling hydrothermal fluid caused the brown cores to become unstable compared with the Fe-rich blue tourmaline rims.

Accessory tourmaline in metasediments from the Sinai crystalline basement exhibits textural and chemical signatures that relate to the evolution of regional metamorphism and deformation during the Pan-African orogeny and testifies to different P-T path segments. Tourmaline inclusions in various porphyroblasts were formed during the prograde phase of metamorphism; acicular to prismatic crystals in the matrix, oriented sub-parallel to, and enveloped by, the main foliation crystallized syntectonically under prograde and peak metamorphic conditions; tourmaline cross-cutting the main foliation may have formed just after the peak or during the retrograde phase of metamorphism. Some of the cores in tourmaline crystals, showing different colours, are interpreted as former detrital grains. The abundance of tourmaline decreases with increasing peak metamorphic conditions. The tourmaline investigated belongs to the schorl-dravitess group, generally with XMg of 0.42–0.73 and XCa = Ca/(Ca+Na+K+□) of 0.02–0.24, typical of tourmalines in metapelites and metapsammites; whereas detrital cores have been derived from various sources, including former tourmaline-quartz and pre-existing high-metamorphic rocks. Tourmaline of the Sinai metasediments was formed during metamorphism of the sedimentary precursors, essentially in a closed system, where clay minerals and organic matter, together with detrital tourmaline, served as the source of boron. Although a metamorphic facies should be defined by characteristic mineral assemblages present in metamorphic rocks, tourmaline chemistry is a good monitor of P-T conditions in the metapelites and semi-metapelites investigated, showing an increase in XMg with increasing metamorphic grade, where XturMg = 0.60 distinguishes between greenschist and lower-amphibolite facies, while XturMg = 0.65 could distinguish lower- from middle- to upper-amphibolite facies. The results of tourmaline-biotite geothermometry compare well with our former temperature estimates using conventional geothermometry and phase-diagram modelling.

Bond-valence theory is used to explore the local arrangements involving vacancies at the Y and Z sites in the tourmaline structure. The local bond-valence requirements of all possible local arrangements around the O8, O7, O6, O3 and O1 anion-sites have been determined for Y- and Z-site vacancies locally associated with Li1+, Mg2+, Al3+, Fe2+, Fe3+, B3+ and Si4+. The results show that arrangements involving tetrahedrally coordinated TR3+-cations and octahedrally coordinated YR2+- and ZR2+-cations around O8, 07 and O6 can be ruled out, together with arrangements involving vacancies and YLi1+. As the occurrence of a Y-site vacancy (Y☐) is more in accord with the valence-sum rule than the occurrence of a Z-site vacancy (Z☐), Y☐ is more likely to occur than Z☐ in tourmaline. Local arrangements involving vacancies around O1- and O3-sites can be stable for OH−, but not for O2−. Of particular interest in this regard are the arrangements [YR3+YR3+Y☐]−O1(OH−) and [ZR3+ZR3+Y☐]−O3(OH−), which yield the smallest deviations from the valence-sum rule. Coupling these stable arrangements with 2 × [TSi4+ZR3+Y☐]−O6(O2−) forms larger vacancy clusters: [Y(R3+)2−O1(OH−)−y(☐)− O3(OH−)−O6(O2−)2−(ZR3+TSi4+)2]. In tourmaline, vacancies are more favoured to occur at Y rather than at Z, in tandem with OH− at O3 and O1, R3+ at Y and Z and Si4+ at T.

Analyses of tourmaline and coexisting muscovite in tourmaline-bearing rocks from SE Ireland indicate that the content of Si in tourmaline is not fixed but is dependent on bulk chemistry, varying inversely with Al. Zoning patterns within tourmaline reflect this and, despite theoretical objections, substitution of Si by Al in the tetrahedral site must occur in nature. Ti may also substitute for Si. Ca and Ti are generally involved in a coupled substitution. Estimates of the degree of alkali-defect and proton-loss substitution in SE Ireland tourmalines indicate that the former process is at least as important as the latter and that bulk chemistry is important in determining which substitution occurs. The general importance of alkali-defect substitution and Al⇌Si suggests that the most useful way to treat microprobe data for schorl-dravite tourmalines is to assume the presence of 3B and 4(OH) and calculate on the basis of 24.5 oxygen atoms.

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.

The stabilities of possible Y(R3+ + R2+ + Li+) clusters around the W anion (O1 site) of the tourmaline structure were checked using the bond-valence approach. Arrangements involving R3+ = Al3+ or Fe3+ and R2+ = (Fe, Mn, Mg)2+ were all found to be stable. Structural data show a strong linear correlation between the mean formal valence (MFV) of the Y cations and the long-range average bond valence sum (BVS) at the O1 site, as estimated from bond-valence parameters. This correlation is observed for all chemical compositions of tourmaline, except for fluor-buergerite where the O3 site is dominated by oxygen anions. Results show that the long-range site populations of the Y and O1 sites are related to each other by valence constraints described by the empirical and theoretical equations: BVS(O1) = [0.99 MFV(Y) − 1.20] and MFV(O1) = [1.00 MFV(Y) − 1.00], respectively. The systematic deviation of the empirical equation from the ideal one is ascribed to the occurrence of bond strain involving the O1 site. An important implication of the correlation between MFV(Y) and BVS(O1) is that the (OH) content at the O1 site may be estimated by the equation W(OH) = 2 − [1.01 BVS(O1)] − 0.21 − F.

The Li and B isotopic compositions of gem-quality Cu-bearing tourmalines were used (1) to distinguish among Paraiba tourmalines from Brazil and Cu-bearing tourmalines from Nigeria and Mozambique; and (2) to identify the likely source of Li and B for these gem-quality tourmalines. The δ11B values of tourmaline from Paraiba, Brazil, range from –42.4‰ to –32.9‰, whereas the δ11B values of Cu-bearing tourmaline from Nigeria and Mozambique range from –30.5‰ to –22.7‰ and –20.8‰ to –19.1‰ respectively. Tourmalines from each locality have relatively homogeneous δ11B values and display no overlap. There is slight overlap between δ7Li values of Paraiba tourmaline (+24.5‰ to +32.9‰) and Cu-bearing tourmaline from Nigeria (+32.4‰ to +35.4‰), and δ7Li values of Cu-bearing tourmaline from Nigeria and Mozambique (+31.5‰ to +46.8‰). Nevertheless, Cu-bearing tourmalines from each locality can be fingerprinted using a combination of their δ11B and δ7Li values. The very small δ11B values are consistent with a non-marine evaporite source, and are among the smallest reported for magmatic systems, expanding the global range of B isotopicc omposition for tourmaline by 12‰. The corresponding large δ7Li values are among the largest reported, although they are less diagnostic of the source of the Li. The large δ7Li values in conjunction with the small δ11B values suggest a non-marine evaporite or brine as a source for Li and B, either as constituent(s) of the magma source region or, by assimilation during magma ascent. The large range in δ11B and δ7Li values suggests that B and Li isotope fractionation occurred during magmatic degassing and late-stage magmatic-hydrothermal evolution of the granite-pegmatite system.

A variety of mushroom tourmaline from the Kat Chay mine, Momeik, near Mogok, Shan state, Myanmar, consists of a black-to-grey single-crystal core from which a single prismatic crystal reaches to the edge of the mushroom, forming a slight protuberance. The rest of the mushroom (∼50% by volume) consists of extremely acicular sub-parallel crystals that diverge toward the edge of the mushroom. The acicular crystals are dominantly colourless to white, with a continuous black zone (2 mm across) near the edge, and pale pink outside the black zone. The composition varies from ∼Na0.75Ca0.05(Li0.80Al0.70Fe1.10.Mn0.30Ti0.10)Al6Si6(B03)3O18(OH)3(OH,F) at the base of the mushroom to ∼Na0.60Ca0.06(Li1.00Al1.98Fe0.02)Al6(Si5.35B0.65)(BO3)3O18(OH)3(OH,F) close to the edge at the top of the mushroom. The principal substitutions are: (1) YLi + YAl -> yFe* + yFe* and (2) TB + yAl -> Si + yFe*, but there are five other minor substitutions that are also operative. There are six significant compositional discontinuities at textural boundaries in the mushroom, suggesting that the changes in habit are driven in part by changes in external variables such as T and P, plus possible involvement of new fluid phases.

Cu-bearing elbaite from Paraíba (Brazil) is a highly-prized gem tourmaline. Specimens of similar quality from localities in Mozambique and Nigeria are being sold, and reliable provenance tools are required to distinguish specimens from the original locality from ‘Paraíba-type’ tourmaline from Africa. Here we present Li and B isotope analyses of Cu-bearing elbaite from all three localities and demonstrate the suitability of these isotope systems as a provenance tool. Isotopic profiles across chemically zoned grains revealed homogenous B and Li isotopic compositions, demonstrating a strong advantage of their application as a provenance tool as opposed to major, minor or trace element signatures.

Li and B isotopes of all investigated samples of Cu-bearing elbaites from the three localities are within the range of previously published granitic and pegmatitic tourmaline. Anomalous isotope compositions published previously for these samples are corrected by our results.