Heflikite, the first Sc-dominant epidote-supergroup mineral, was discovered in two occurrences. The holotype was found in a granitic pegmatite associated with rodingite-like calc-silicate rocks and metasomatised granitic bodies exposed in a serpentinite quarry at Jordanów Śląski near Sobótka, Lower Silesia, SW Poland. The cotype comes from the Heftetjern pegmatite, Tørdal region, Norway. The holotype is composed of (in wt.%): 35.69 SiO2, 0.22 TiO2, 21.98 Al2O3, 6.12 Sc2O3, 0.07 V2O3, 1.10 Fe2O3, 0.11 Y2O3, 1.55 La2O3, 4.05 Ce2O3, 0.31 Pr2O3, 1.53 Nd2O3, 0.40 Sm2O3, 0.11 EuO, 0.56 Gd2O3, 0.14 MnO, 3.56 FeO, 0.16 MgO, 19.16 CaO and 1.78 H2O(+)calc.; total 98.60. The cotype contains: 34.92 SiO2, 0.44 TiO2, 0.82 SnO2, 19.13 Al2O3, 4.79 Sc2O3, 1.96 Fe2O3, 2.55 La2O3, 7.39 Ce2O3, 0.48 Pr2O3, 0.67 Nd2O3, 0.12 EuO, 0.61 Gd2O3, 0.13 MnO, 5.97 FeO, 17.66 CaO and 1.73 H2O(+)calc.; total 99.37. The compositions correspond to the following empirical formulae: (Ca1.729Ce0.125La0.048Nd0.046Gd0.016Sm0.012Pr0.010Y0.005Eu2+0.003)Σ1.994[(Al2.182Sc0.449Fe3+0.070V3+0.005)Σ2.706(Fe2+0.251Mg0.020Mn0.010)Σ0.281Ti0.014]Σ3.001(Si3.006O11)O(OH) and (Ca1.644Ce0.235La0.082Nd0.021Gd0.018Pr0.015Eu2+0.004)Σ1.019[(Al1.958Sc0.362Fe3+0.128)Σ2.448(Fe2+0.434Mn0.009)Σ0.443(Ti0.029Sn0.029)Σ0.058]Σ2.949(Si3.033O11)O(OH), respectively, and to the ideal formula Ca2(Al2Sc)(Si2O7)(SiO4)O(OH). The crystal structure of the holotype was refined in the monoclinic system with an R1 index of 8.62%. The crystal-structure refinement indicates exclusively Si occupied T sites, Al occupied M1 and M2 sites, and a Ca occupied A1 site. The M3 site is filled predominantly by trivalent cations, mainly Sc3+, with divalent cations (mainly Fe2+) as minor occupants. The A2 site is filled mostly by Ca with minor amounts of rare earth elements (REE). The holotype heflikite crystallised from metasomatic fluids that infiltrated a contact between the granitic pegmatite and the surrounding rodingite-type calc-silicate rocks and serpentinites. The fluids that introduced Sc into the pegmatite could have been either hydrothermal or related to low-grade regional metamorphism that postdated the formation of the pegmatite. The cotype heflikite formed during the late-stage hydrothermal crystallisation of the Sc-enriched granitic pegmatite.

Five povondraite crystals from San Francisco Mine, Villa Tunari, Bolivia, have been structurally and chemically characterised by single-crystal X-ray diffraction and electron microprobe analysis. For the first time, this characterisation is accompanied by Mössbauer spectroscopic and single-crystal infrared spectroscopic data, which show the exclusive presence of Fe3+ at both the octahedrally-coordinated Y and Z sites as well as slight disorder of (OH) and O over the O(1) and O(3) sites.

The data obtained along with those for earlier-studied bosiite and oxy-dravite oxy-tourmalines show a complete substitution series described by the reaction YFe3+3 + ZMg + ZFe3+4 ↔ YAl2 + YMg + ZAl5 (i.e. Fe3+Al–1) with variation of the structural parameters dominated by Fe3+ (or Al). Povondraite is the tourmaline member having the largest unit-cell parameters due to the larger size of Fe3+ relative to other trivalent cations (V > Cr > Al). In the tourmaline-supergroup minerals, the a and c unit-cell parameters vary from ~15.60 Å to ~16.25 Å and ~7.00 Å to ~7.50 Å, respectively. Their values increase with increasing Fe3+ or decreasing Al. End-member compositions related to the smallest and largest a and c parameters are, respectively, NaAl3Al6(Si3B3O18)(BO3)3(OH)3(OH) (synthetic tourmaline) and NaFe3+3(Fe3+4Mg2)(Si6O18)(BO3)3(OH)3O (povondraite).

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:

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

Princivalleite, Na(Mn2Al)Al6(Si6O18)(BO3)3(OH)3O, is a new mineral (IMA2020-056) of the tourmaline supergroup. It occurs in the Veddasca Valley, Luino area, Varese, Lombardy, Italy (46°03’30.74’’N, 8°48’24.47’’E) at the centre of a narrow (2–3 cm wide) vertical pegmatitic vein, a few metres long, crosscutting a lens of flaser gneiss. Crystals are subhedral (up to 10 mm in size), azure with a vitreous lustre, conchoidal fracture and white streak. Princivalleite has a Mohs hardness of ~7, a calculated density of 3.168 g/cm3 and is uniaxial (–). Princivalleite has trigonal symmetry, space group R3m, a = 15.9155(2) Å, c = 7.11660(10) Å, V = 1561.15(4) Å3 and Z = 3. The crystal structure was refined to R1 = 1.36% using 1758 unique reflections collected with MoKα X-ray intensity data. Crystal-chemical analysis resulted in the empirical crystal-chemical formula

X(Na0.54Ca0.11□0.35)Σ1.00Y(Al1.82Mn2+0.84Fe2+0.19Zn0.07Li0.08)Σ3.00Z(Al5.85Fe2+0.13Mg0.02)Σ6.00[T(Si5.60Al0.40)Σ6.00O18](BO3)3O(3)[(OH)2.71O0.29]Σ3.00O(1)[O0.66F0.22(OH)0.12]Σ1.00 which recast in its ordered form for classification purposes is:

X(Na0.54Ca0.11□0.35)Σ1.00Y(Al1.67Mn2+0.84Fe2+0.32Zn0.07Mg0.02Li0.08)Σ3.00ZAl6.00[T(Si5.60Al0.40)Σ6.00O18](BO3)3V[(OH)2.71O0.29]Σ3.00W[O0.66F0.22(OH)0.12]Σ1.00.

Princivalleite is an oxy-species belonging to the alkali group of the tourmaline supergroup. The closest end-member compositions of valid tourmaline species are those of oxy-schorl and darrellhenryite, to which princivalleite is related by the substitutions Mn2+ ↔ Fe2+ and Mn2+ ↔ 0.5Al3+ + 0.5Li+, respectively. Princivalleite from Veddasca Valley is a geochemical anomaly, originated in a B-rich and peraluminous anatectic pegmatitic melt formed in situ, poor in Fe and characterised by reducing conditions in the late-stage metamorphic fluids derived by the flaser gneiss. The Mn-enrichment in this new tourmaline is due to absence of other minerals competing for Mn such as garnet.

A gem-quality purplish-red tourmaline sample of alleged liddicoatitic composition from the Anjanabonoina pegmatite, Madagascar, has been fully characterised using a multi-analytical approach to define its crystal-chemical identity. Single-crystal X-ray diffraction, chemical and spectroscopic analysis resulted in the formula: X(Na0.41□0.35Ca0.24)Σ1.00Y(Al1.81Li1.00Fe3+0.04Mn3+0.02Mn2+0.12Ti0.004)Σ3.00ZAl6 [T(Si5.60B0.40)Σ6.00O18] (BO3)3 (OH)3W[(OH)0.50F0.13O0.37]Σ1.00 which corresponds to the tourmaline species elbaite having the typical space group R3m and relatively small unit-cell dimensions, a = 15.7935(4) Å, c = 7.0860(2) Å and V = 7.0860(2) Å3.

Optical absorption spectroscopy showed that the purplish-red colour is caused by minor amounts of Mn3+ (Mn2O3 = 0.20 wt.%). Thermal treatment in air up to 750°C strongly intensified the colour of the sample due to the oxidation of all Mn2+ to Mn3+ (Mn2O3 up to 1.21 wt.%). Based on infrared and Raman data, a crystal-chemical model regarding the electrostatic interaction between the X cation and W anion, and involving the Y cations as well, is proposed to explain the absence or rarity of the mineral species ‘liddicoatite’.

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.

Potassic-jeanlouisite, ideally K(NaCa)(Mg4Ti)Si8O22O2, is the first characterised species of oxo amphibole related to the sodium–calcium group, and derives from potassic richterite via the coupled exchange CMg–1W${\rm OH}_{{\rm \ndash 2}}^{\ndash}{} ^{\rm C}{\rm Ti}_1^{{\rm 4 +}} {} ^{\rm W}\!{\rm O}_2^{2\ndash} $. The mineral and the mineral name were approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification, IMA2018-050. Potassic-jeanlouisite was found in a specimen of leucite which is found in the lava layers, collected in the active gravel quarry on Zirkle Mesa, Leucite Hills, Wyoming, USA. It occurs as pale yellow to colourless acicular crystals in small vugs. The empirical formula derived from electron microprobe analysis and single-crystal structure refinement is: A(K0.84Na0.16)Σ1.00B(Ca0.93Na1.02Mg0.04${\rm Mn}_{{\rm 0}{\rm. 01}}^{2 +} $)Σ2.00C(Mg3.85${\rm Fe}_{{\rm 0}{\rm. 16}}^{2 +} $Ni0.01${\rm Fe}_{{\rm 0}{\rm. 33}}^{3 +} {\rm V}_{{\rm 0}{\rm. 01}}^{3 +} $Ti0.65)Σ5.01T(Si7.76Al0.09Ti0.15)Σ8.00O22W[O1.53F0.47]Σ2.00. The holotype crystal is biaxial (–), with α = 1.674(2), β = 1.688(2), γ = 1.698(2), 2Vmeas. = 79(1)° and 2Vcalc. = 79.8°. The unit-cell parameters are a = 9.9372(10), b = 18.010(2), c = 5.2808(5) Å, β = 104.955(2)°, V = 913.1(2) Å3, Z = 2 and space group C2/m. The strongest eight reflections in the powder X-ray pattern [d values (in Å) (I) (hkl)] are: 2.703 (100) (151); 3.380 (87) (131); 2.541 (80) ($\bar 2$02); 3.151 (70) (310); 3.284 (68) (240); 8.472 (59) (110); 2.587 (52) (061); 2.945 (50) (221,$\bar 1$51).

Two crystals from a sample of titanite from the Heftetjern granitic pegmatite, Tørdal, southern Norway, were extracted for structure analysis and shown to have triclinic symmetry. Unit-cell parameters are as follows: a = 7.0696(4) Å, b = 8.7167(5) Å, c = 6.5695(3) Å, α = 89.7372(11)°, β = 113.7607(10)°, γ = 90.2929(13)°, V = 370.52(6) Å3 for one crystal and a = 7.0612(5) Å, b = 8.7102(6) Å, c = 6.5628(4) Å, α = 89.7804(16)°, β = 113.7713(13)°, γ = 90.2502(16)°, V = 369.39(7) Å3 for the other. The interaxial angles α and γ deviate from the value of 90° required for monoclinic symmetry by ~200–250 standard deviations. The single-crystal X-ray intensities were averaged in both monoclinic and triclinic Laue symmetries, giving R(merge) values of ~14% and ~1.3% respectively. For both crystals, more than 50 reflections with I > 3σI violated the criterion for the presence of the a-glide required for monoclinic A2/a symmetry. Both crystals were refined in the space group A with Z = 4, and final R1 indices are 4.4% and 4.7% (wR2 = 8.4 and 8.9%) respectively. The composition of one crystal was determined by electron microprobe analysis: Ca[Ti0.623Ta0.105Nb0.018Al0.137Fe0.0463+Sn0.0834+]Σ=1.012(SiO4)O. The characteristic corner-sharing [MO5] chains of identical octahedra observed in monoclinic titanite become chains of alternating M(1) and M(2) octahedra of different size, with the stronger X-ray scattering constituents concentrated at the M(2) site. Short-range bond-valence considerations suggest that the M cations will order as Al—O—Ta in adjacent octahedra, and when present in sufficient amounts, will couple along the chain to break long-range monoclinic symmetry.

Natrotitanite, ideally (Na0.5Y0.5)Ti(SiO4)O, is a new mineral from the Verkhnee Espe rare-element deposit at the northern exo-contact of the Akjailyautas granite massif in the northern part of the Tarbagatai mountain range, Eastern Kazakhstan. Both the mineral and the name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA 2010-033). Star-shaped aggregates of small short prisms of yellow or yellowish white (Na,Y,REE)-bearing titanite rimmed by thin (∼2 μm) rims of natrotitanite are embedded in yttrium-bearing fluorite and replace narsarsukite. Associated minerals are microcline, albite, quartz, riebeckite, aegirine, biotite, astrophyllite, rutile, zircon and elpidite. Natrotitanite is milky white to yellowish grey, transparent to translucent, and has a white streak and a vitreous lustre. It shows pale orange cathodoluminescence but does not fluoresce under ultraviolet light. It shows no cleavage or parting, and is brittle; the calculated density is 3.833 g cm–3. The indices of refraction, measured with the Bloss spindle stage for the wavelength 590 nm using a gel filter, are α = 1.904, γ = 2.030, and these values are in accord with the mean refractive index, 1.988, calculated from the Gladstone-Dale relation. Natrotitanite is monoclinic, C2/c, a = 6.5691(2), b = 8.6869(3), c = 7.0924(2) Å, β = 114.1269(4)°, V = 369.4(2) Å3, Z = 4, a:b:c = 0.7562:1: 0.8164. The seven strongest lines in the X-ray powder diffraction pattern [in the order d (Å), I, (hkl)] are as follows: 2.597, 10, (130); 3.248, 8, (11); 2.994, 6, (200); 1.641, 4, (330); 4.941, 3, (110); 1.498, 3, (400); 2.273, 3, (11). Chemical analysis by electron microprobe gave Nb2O5 1.28, SiO2 27.83, TiO2 35.00, SnO2 0.57, V2O3 0.36, Fe2O3 0.23, Y2O3 7.87, Ce2O3 0.83, Sm2O3 0.26, Gd2O3 0.46, Tb2O3 0.17, Dy2O3 2.45, Ho2O3 0.16, Er2O3 2.24, Tm2O3 0.50, Yb2O3 2.53, Nd2O3 0.35, Lu2O3 0.28, MnO 0.33, CaO 8.16, Na2O 5.55, F 1.52 O ≡ F –0.64, sum 98.71 wt.%. The resulting empirical formula is (Na0.39Ca0.32Y0.15Dy0.03Yb0.03Er0.03Ce0.01Ho0.01Tm0.01Gd0.01Nd0.01)Σ1.00(Ti0.95Nb0.02Sn0.01Fe3+0.01Mn0.01V0.01)Σ1.01Si1.01O4.00(O0.83F0.17), calculated on the basis of 3 cations per formula unit. The general formula is written as (Na,Ca,Y,REE)TiSiO4(O,F), and the endmember formula is (Na0.5Y0.5)Ti(SiO4)O.

The crystal structure of a composite optically continuous crystal of natrotitanite and (Na, Y)-bearing titanite was mounted on a Bruker D8 three-circle diffractometer equipped with a rotating anode generator (MoKα radiation), a multi-layer optics incident-beam path and an APEX-II CCD detector. The crystal structure was refined in space group C2/c to a final R1 index of 1.8%. Natrotitanite is isostructural with titanite, (Na + Y + REE) replacing Ca at the Ca site in the titanite structure.

Fluoro-aluminoleakeite, ideally , is a new mineral of the amphibole group from Norra Kärr, Sweden (IMA-CNMMNC 2009-012). It occurs in a proterozoic alkaline intrusion that mainly comprises a fine-grained schistose agpaitic nepheline-syenite (grennaite). Fluoro- aluminoleakeite occurs as isolated prismatic crystals 0.10–2 mm long in a syenitic matrix. Crystals are light greenish-blue with a greenish-blue streak. It is brittle, has a Mohs hardness of 6 and a splintery fracture; it is non-fluorescent with perfect {110} cleavage, no observable parting, and has a calculated density of 3.14 g cm–3. In plane-polarized light, it is pleochroic, X = pale green, Y = dark green, Z = pale green; X ^ a = 62.9° (in β obtuse), Y || b. Fluoro-aluminoleakeite is biaxial negative, α = 1.632(1), β = 1.638(1), γ = 1.643(1); 2Vobs. = 98.0(4)°, 2Vcalc. = 95.5°.M

Fluoro-aluminoleakeite is monoclinic, space group C2/m, a = 9.7043(5) Å, b = 17.7341(8) Å, c = 5.2833(3) Å, β = 104.067(4)°, V = 882.0(2) Å3, Z = 2. The eight strongest X-ray diffraction lines in the powder-diffraction pattern are [d in Å, (I), (hkl)]: 2.687, (100), (31, 151); 4.435, (80), (021, 040); 3.377, (80), (131); 2.527, (60), (02); 8.342, (50), (110); 3.096, (40), (310); 2.259, (40), (71, 12) and 2.557, (30), (002, 061). Analysis, by a combination of electron microprobe and crystal-structure refinement, gives SiO2 58.61, Al2O3 7.06, TiO2 0.32, FeO 3.27, Fe2O3 6.05, MgO 8.61, MnO 0.73, ZnO 0.43, CaO 0.05, Na2O 9.90, K2O 2.43, Li2O 1.62, F 3.37, H2Ocalc. 0.50, sum 101.08 wt.%. The formula unit, calculated on the basis of 24 (O,OH,F,Cl) p.f.u. with (OH) + F = 2 a.p.f.u., is A(Na0.65 O22W(F1.47OH0.53)Σ=2.00. Crystal-structure analysis shows CLi to be completely ordered at the M(3) site, and provided reliable site populations. Fluoro-aluminoleakeite is related to the end-member leakeite, , by the substitutions CFe3+ → CAl and WF → W(OH).

The crystal structures of twenty-five orthorhombic Fe-Mg-Mn amphiboles, a = 18.525 – 18.620, b = 17.806-18.034, c = 5.264-5.303 Å, V = 1737.6-1776.7, space group = Pnma, Z = 4, have been refined to R indices in the range 2.1–7.8% using 790–1804 unique observed reflections measured with Mo-Kα X-radiation on a Bruker P4 automated four-circle diffractometer equipped with a 1K CCD detector. The quality of the refinements is strongly a function of the [4]Al content of the crystals because of unmixing in the central part of the series due to the presence of a low-temperature solvus. The amphibole crystals were analysed by electron microprobe subsequent to collection of the X-ray intensity data and span the anthophyllite-gedrite series from 0.17–1.82 [4]Al a.p.f.u. Mössbauer spectroscopy shows that the amphiboles of this series commonly contain small but significant amounts of Fe3+ . The amount of [4]Al is linearly related to the grand <T-O> distance by the equation <T-O> = 1.6214 + 0.171 [4]Al, R = 0.980; the slope of this relation is not significantly different from that characteristic of a hard-sphere model. The <T-O> distances indicate the following site preference for [4]Al: T1B > T2B > T1A » T2A. The <M2-O> distances are compatible with all [6]Al and Fe3+ ordered at the M2 site. The grand <M1,2,3 '3 –O> distance is related to the mean radius of the constituent cations, <rM1,2,3>, by the equation ≪M1,2,3-O≫ = 1.4684 + 0.8553(7) <rM1,2,3>.

Fluoroleakeite, NaNa2(Mg2Fe3+2Li)Si8O22F2 is a new mineral of the amphibole group from the Verkhnee Espe deposit, Akjailyautas mountains, eastern Kazakhstan district, Kazakhstan. The granites and their host rocks have been intensely reworked by post-magmatic and host-rock fluids, resulting in intense recrystallization, enrichment in F, Li and rare elements, and replacement of primary biotite and sodic-calcic amphiboles by Li-bearing riebeckite, aegirine, astrophyllite and other sodic minerals including fluoroleakeite. Crystals are prismatic parallel to [001] with {100} and {110} faces and cleavage surfaces, and the prism direction is terminated by irregular fractures. Grains are up to 3 mm long, and occur as isolated crystals, as small aggregates, and as inclusions in cámaraite. Crystals are black with a very pale grey to colourless streak. Fluoroleakeite is brittle, has a Mohs hardness of 6 and a splintery fracture; it is non-fluorescent with perfect {110} cleavage, no observable parting, and has a calculated density of 3.245 g cm–3. In plane-polarized light, it is pleochroic, X = pale grey-green, Y = medium grey, Z = grey-brown; X^a = 14.1° (in β obtuse), Y ‖ b, Z^c = 75.9° (in β acute). Fluoroleakeite is biaxial negative, α = 1.663(2), β = 1.673(2), γ = 1.680(2); 2Vobs = 80.9(6)°, 2Vcalc = 79.4°

Fluoro-leakeite is monoclinic, space group C2/m, a = 9.8927(3), b = 17.9257(6), c = 5.2969(2) Å, β = 103.990(1)°, V = 905.7(1) Å3, Z = 2. The strongest ten X-ray diffraction lines in the powder pattern are [d in Å(I)(hkl)]: 2.718(100)(151), 8.434(40)(110), 4.464(30)(021), 3.405(30)(131), 3.137(20)(310), 2.541(20)(), 2.166(20)(261), 2.325(15)(), 2.275(15)() and 2.806(10)(330). Analysis by a combination of electron microprobe and crystal-structure refinement gives SiO2 53.34, Al2O3 0.62, TiO2 1.27, V2O3 0.05, Fe2O3 15.10, FeO 6.00, MnO 2.04, ZnO 0.18, MgO 6.40, CaO 0.13, Na2O 9.08, K2O 1.98, Li2O 1.10, F 3.33, H2Ocalc 0.16, sum 99.39 wt.%. The formula unit, calculated on the basis of 23 O, is A(Na0.64K0.38)(Na1.98Ca0.02)(Li0.66Mg1.42Fe0.752+Mn0.262+Zn0.02Fe1.693+V0.013+Ti0.144+Al0.03) (Si7.93Al0.07)O22(F1.57OH0.16O0.27). Crystal-structure refinement shows Li to be completely ordered at the M(3) site. Fluoroleakeite, ideally NaNa2(Mg2Fe23+Li)Si8O22F2, is related to end-member leakeite, NaNa2(Mg2Fe23+Li)Si8O22(OH)2 by the substitution F → (OH).

The crystal chemistry of a natural, gem-quality, blue-grey Zn-rich spinel crystal from Jemaa, Kaduna State, Nigeria, was studied using electron microprobe, single-crystal X-ray diffraction, optical absorption and Raman spectroscopies. The composition of the crystal approaches the gahnite endmember (ZnAl2O4), ∼94 mol.%, with the remainder being dominated by a hercynite component (FeAl2O4). The unit-cell dimension is 8.0850(3) Å and the tetrahedral and octahedral bond distances are determined as T–O 1.9485(6) Å and M–O 1.9137(3) Å. Crystal chemical analysis resulted in the empirical structural formula T(Zn0.94Fe2+0.03Al0.03)M (Al1.96Fe2+0.03Fe3+0.01)O4, which shows Zn and Al almost fully ordered in the tetrahedrally and octahedrally coordinated T and M sites, respectively. Raman spectra obtained using the excitation of the blue 473.1 nm line of a Nd:YAG laser display three of the five Raman-active modes predicted for the general oxide spinel group of minerals. These are the Eg mode at 420.6 cm–1 and the T2g modes at 510 cm–1 and 661 cm–1, due to vibrations in the AlO6 octahedra. Optical absorption spectra recorded in the UV/VIS-NIR-MIR range 2000 29000 cm–1 show a dominant absorption band at ∼5000 cm–1 which is caused by spin-allowed electronic d–d transitions in Fe2+ located at the T sites. The blue-grey hue exhibited by the sample is mainly due to spin-forbidden electronic transitions in TFe2+ and to MFe2+ ↔MFe3+ intervalence charge transfer, and the poor saturation of the colour is due to the small concentration of Fe2+ and Fe3+.

Bavenite is an orthorhombic calcium beryllium aluminosilicate, a ≈ 23.2, b ≈ 5.0, c ≈ 19.4 Å, V ≈ 2250 Å3, Z = 4, that crystallizes in the space group Cmcm. The crystal structures of 24 bavenite samples from various localities worldwide were refined to R1 values from 2.4 to 7.5% based on ∼1330 unique reflections collected with Mo-Kα X-radiation on a Bruker P4 CCD single-crystal diffractometer. The composition of each crystal was determined by electron microprobe analysis. There is extensive solid-solution in bavenite according to O(2)OH– + T(4)Si4+ + T(3)Be2+ ⇌ O(2)O2– + T(4)Al3+ + T(3)Si4+, such that the general formula may be written Ca4BexSi9Al4–xO28–x(OH)x, where x ranges from 2.00 to ∼3.00 a.p.f.u. Small amounts of additional Be may be incorporated into bavenite via the substitution T(3)Be + O(2)OH– + Na + T(4)Si2 ⇌ T(3)Si + O(2)O2– + Ca + T(4)Al2. Local (short-range) bond-valence considerations indicate that Short-Range Order (SRO) should be extensive in the bavenite structure, and this is confirmed by Fourier Transform Infrared (FTIR) spectroscopy in the principal OH-stretching region and by 27Al Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectroscopy. Short-range bond-valence considerations indicate that the T(3)–T(4)–T(3)–T(4) rings of the framework can incorporate any short-range arrangement of cations consonant with their site populations [T(3) = Be,Si; T(4) = Si,Al], and 27Al MAS NMR spectroscopy confirms this, showing the presence of the local clusters T(3)Be–T(4)Al–T(3)Be, T(3)Si–T(4)Al–T(3)Be and T(3)Si–T(4)Al–T(3)Si. Incorporation of Be at the T(3) site is accompanied by local replacement of O2– by (OH)– at the O(2) site and hydrogen bonding to the adjacent O(3) anion; the latter promotes Be → Si substitution at the T(3) tetrahedron adjacent in the b direction. T(3)–T(4)–T(3)–T(4) rings link in the c direction through a T(3)–(1)–(3) linkage [T(1) = Si]. Local bond-valence considerations show that occupancy of both T(3) tetrahedra by Be violates the valence-sum rule, and that the linkage T(3)Be–T(1)Si–T(3)Si provides the constraint whereby Be does not exceed 3 a.p.f.u. in bavenite when incorporated via the substitution O(2)OH– + T(4)Si4+ + T(3)Be2+ ⇌ O(2)O2– + T(4)Al3+ + T(3)Si4+.

The crystal structure of mosandrite, ideally (Ca3REE)[(H2O)2Ca0.5☐0.5]Ti(Si2O7)2(OH)2(H2O)2, from the Saga mine, Morje, Porsgrunn, Norway, has been refined as two components related by the TWIN matrix ( 0 0, 0 0, 1 0 1): a 7.4222(3), b 5.6178(2), c 18.7232(7) Å, β 101.4226(6)°, V = 765.23(9) Å3, space group P21/c, Dcalc. = 3.361 g.cm–3, R1 = 3.69% using 1347 observed (Fo > 4σF) reflections. The empirical formula of mosandrite (EMPA) was calculated on the basis of 4 Si a.p.f.u., with H2O determined from structure refinement: [(Ca2.89Ba0.01)Σ2.90(Ce0.39La0.18Nd0.14Sm0.02Gd0.03Y0.16Th0.03)Σ1.01Zr0.09]Σ4 [(H2O)2.00Ca0.32Na0.17Al0.10Mn0.04Fe2+0.02☐0.35]Σ3(Ti0.87Nb0.09Zr0.04)Σ1(Si2O7)2[(OH)1.54F0.46]Σ2[(H2O)1.50F0.50]Σ2, Z = 2. The crystal structure of mosandrite is a framework of TS (titanium silicate) blocks; each TS block consists of HOH sheets (H-heteropolyhedral, O-octahedral). In the TS block, there are five fully occupied cation sites, two [4]-coordinated Si sites with <Si–O> 1.623 Å , [7]-coordinated MH and AP sites occupied by Ca and REE in the ratio ∼3:1, and one [6]-coordinated Ti-dominant MO(1) site. There are two H2O-dominant H2O-alkali-cation sites. The partly occupied MO(2) site has composition [(H2O)0.5☐0.33Na0.17], ideally [(H2O)0.5☐0.5] p.f.u. The MO(3) site has ideal composition [(H2O)1.5Ca0.5] p.f.u. In the O sheet, the XOM and XOA anion sites have compositions [(OH)1.54F0.46] (XOM) and [(H2O)1.50F0.50] (XOA), ideally (OH)2 and (H2O)2 p.f.u. The MH and AP polyhedra and Si2O7 groups constitute the H sheet that is completely ordered. In the O sheet, MO(1) octahedra are long-range ordered whereas H2O and OH groups and alkali cations Na and Ca are long-range disordered. Two SRO (short-range ordered) arrangements have been proposed for the O sheet: (1) Na [MO(2)], Ca2 [MO(3)] and F4[XOM and XOA anion sites]; (2) 2 H2O [MO(2)] and MO(3)] and (OH)2 and (H2O)2 [XOM and XOA]. Linkage of H and O sheets occurs mainly via common vertices of MH polyhedra and Si2O7 groups and MO(1) octahedra. Two adjacent TS blocks are related by the glide plane cy. Mosandrite is an H2O- and OH-bearing Na- and Ca-depleted analogue of rinkite, ideally (Ca3REE)Na(NaCa) Ti(Si2O7)2(OF)F2. Mosandrite and rinkite are related by the following substitution at the MO(2,3) and XO(M,A) sites in the O sheet: M[(H2O)2 + ☐0.5] + X[(OH)–2 + (H2O)2] ↔ M[Na+2 + Ca2+0.5] + X[(OF)3– + (F2)2–].

The crystal chemistry of sekaninaite from Dolní Bory, Czech Republic, was characterized by a multimethod approach. Particular emphasis was put on the characterization of the channel constituents (i.e. H2O and CO2). Electron microprobe analysis shows the sample to be close to the Fe endmember [XFe = Fe/(Fe+Mg) = 94%) with significant Mn (1.48 wt.%) present; laser ablation mass-spectrometry showed the presence of 0.42 wt.% Li2O. H2O and CO2 contents (1.48 and 0.17 wt.%, respectively) were determined via secondary-ion mass-spectrometry. Sample homogeneity was checked by Fourier-transform infrared (FTIR) imaging using a microscope equipped with a focal plane array detector. Single-crystal FTIR spectroscopy confirmed the presence of two types of H2O groups in different orientations (with prevalence of the type II orientation), and that CO2 is oriented preferentially normal to the crystallographic c axis. Using the Beer-Lambert relation, integrated molar coefficients, εi, were calculated for both types of H2O (εi H2O[I] = 6000±2000; εi H2O[II] = 13000±1000) and for CO2 (εiCO2 = 2000±1000).

A second occurrence of ferri-fluoro-leakeite has been identified in the Bratthagen nepheline syenite pegmatite (Vestfold County, Norway). With respect to the holotype found at the Verkhnee Espe deposit (Akjailyautas Mountains, Kazakhstan; Cámara et al., 2010), it is closer to the ideal composition because of its larger Li and Mg contents and the absence of an oxo-component; however, it has a significant Zn content (0.29 a.p.f.u.). The ideal formula of ferri-fluoro-leakeite is ANaBNa2 C(Mg2Fe2 3+Li)TSi8O22WF2 and the empirical formula derived from electron-microprobe analysis and single-crystal structure refinement for the sample used here is A(Na0.68K0.32)S=1.00BNa2.00 C(Mg1.69Mn0.25 2+Fe0.24 2+Zn0.29Al0.23Fe1.50 3+Ti0.02Li0.78)S=5.00TSi8O22W(F1.59(OH)0.41)S=2.00. Unitcell data are a = 9.788(2), b = 17.826(3), c = 5.282(1) Å, β = 104.195(5)°, V = 893.5 (3) Å3, Z = 2. Crystal-chemical analysis shows that Li is ordered at the M(3) site and Zn is ordered mainly at the M(2) site, confirming previous findings for Li-bearing amphiboles. The new data also make quantification of the oxo component in Na amphiboles possible.

Noonkanbahite, ideally BaKNaTi2(Si4O12)O2, is described as a new mineral species. At Liley [Löhley], Eifel Mountains, Germany (the holotype locality), it occurs as sprays of prismatic crystals (up to 8 mm) or single prismatic crystals (up to 4 mm) on walls of cavities in alkaline igneous rocks. At Murun, Siberia, Russia, noonkanbahite forms coarse lamellar crystals up to 0.05 cm × 0.7 cm × 1.5 cm embedded in kalsilite syenite. Noonkanbahite is brittle, H = 6, Dobs. = 3.39(1), Dcalc. = 3.49 g/cm3, has a vitreous lustre and does not fluoresce in ultraviolet light. It has poor cleavage on {010} and {100} and weak parting on {011}. Noonkanbahite is biaxial positive with 2Vobs. = 75(2)°, 2Vcalc. = 72.7(9)°, α 1.730(5), β 1.740(5) and γ 1.765(5), dispersion is medium, r < v. In transmitted plane-polarized light, noonkanbahite is strongly pleochroic, with X colourless, Y yellowish, Z straw-yellow; X = a, Y = b, Z = c. Noonkanbahite is orthorhombic, space group Imma, a = 8.0884(4), b = 10.4970(5), c = 13.9372(6) Å, V = 1183.3(1) Å3, Z = 4. The strongest ten X-ray diffraction lines in the powder pattern [d in Å (I)(hkl)] are: 2.907(100)(222), 8.353(50)(001), 3.196(50)(220), 2.097(50)(242), 2.241(40)(215), 2.179(40)(035), 3.377(30)(031), 2.694(30)(015), 2.304(30)(233), and 1.564(30)(064). Electron microprobe analysis gives SiO2 37.82, TiO2 15.54, ZrO2 0.42, Nb2O5 3.18, Al2O3 0.17, Fe2O3 (recalculated from FeO) 5.63, MnO 0.32, MgO 0.53, BaO 20.60, CaO 1.36, K2O 5.32, Na2O 6.14, F 0.78, H2O 0.58, sum 98.39 wt.%, (H2O determined by SIMS). The formula unit, calculated on the basis of 14 anions (O+OH+F), is (Ba0.85K0.13)Σ0.98(K0.59Na0.26Ca0.15)Σ1.00Na(Ti1.23Fe0.453+Nb0.15Mg0.08Mn0.03Zr0.02Al0.01)Σ1.97 (Si3.99Al0.01O12)(O1.33OH0.41F0.26)Σ2.00, Z = 4.

The crystal structure was refined to R1 = 2.8% for 970 unique (F0 > 4σF) reflections collected on a Bruker single-crystal P4 diffractometer with a CCD detector and MoKα X-radiation. The crystal structure of noonkanbahite is isostructural with that of batisite, ideally BaNa2Ti2(Si4O12)O2, and scherbakovite, ideally K2NaTi2(Si4O12)O(OH). There are two octahedrally coordinated sites, M(1) and M(2), occupied by (Ti1.23Fe0.453+Nb0.15Mg0.08Mn0.03Zr0.02Al0.01), ideally Ti2 a.p.f.u. There are three interstitial A sites, [9]A(1), [8]A(2) and [6]A(3), occupied by Ba, K and Na, respectively. Si tetrahedra and M octahedra form a framework with interstitial cages occupied by Ba, K and Na atoms at the A sites. Noonkanbahite, BaKNaTi2(Si4O12)O2, is a K analogue of batisite, BaNa2Ti2(Si4O12)O2, and a Ba analogue of shcherbakovite, K2NaTi2(Si4O12)O(OH).

Fluoro-potassic-pargasite, ideally AKBCa2C(Mg4Al) (Si6Al2)O22WF2, a new amphibole species, has been found in a skarn in the Tranomaro area, Madgascar. The sample used for the description of the new mineral species is a large single amphibole crystal, 4 mm × 2 mm × 2 cm in size, brownish-black with brownish-yellow phlogopite lamellae adhering to one face of the crystal. Fluoro-potassic-pargasite is brittle, has a Mohs hardness of 6.5 and a splintery fracture; it is non-fluorescent, has perfect {110} cleavage, no observable parting, and has measured and calculated densities of 3.46 and 3.151 g cm−3, respectively. In plane-polarized light, it is pleochroic, X = colourless to very pale grey, Y = very pale grey, Z = colourless; X ^ a = 46.9° (in β obtuse), Y ‖ b, Z ^ c = 31.4° (in β acute). It is biaxial positive, α = 1.638(2), β = 1.641(2), γ = 1.653(2); 2Vobs = 49.6(4)°, 2Vcalc = 53.4°.

Fluoro-potassic-pargasite is monoclinic, space group C2/m, a = 9.9104(2), b = 17.9739(4), c = 5.3205(1) Å, β = 105.534(2)°, V = 913.11(6) Å3, Z = 2. The eight strongest lines in the X-ray powder-diffraction pattern are [d in Å(I)(hkl)]: 3.133(100)(310), 3.270(55)(240), 2.809(47)(330). 8.413(45)(110), 2.698(39)(151), 3.374(31)(131), 2.934(29)(221) and 1.647(29)(461). Electron microp-robe analysis gives SiO2 40.20, Al2O3 17.61, TiO2 0.46, FeO 1.96, Fe2O3 2.51, MgO 16.95, MnO 0.05, CaO 13.18, Na2O 0.99, K2O 3.72, F 2.75, H2Ocalc 0.77, sum 99.99 wt.%. The formula unit, calculated on the basis of 24 (O,OH,F) with (OH + F) = 2 - (2 × Ti), is A(K0.69Na0.28Ca0.04)∑=1.01BCa2.00C(Mg3.64Fe0.242+Mn0.01Al0.79Fe0.273+Ti0.05)∑=5.00T(Si5.80Al2.20)∑=8.00O22W[F1.26(OH)0.74]∑=2.00. The mineral species and name have been approved by the IMA CMNMC (IMA 2009-091).

The crystal structure of the mineral coquandite, a rare Sb oxy-sulfate hydrate, was solved using intensity data collected from a crystal from the Cetine mine, Tuscany, Italy. This study revealed that the structure is triclinic, space group P , with a = 11.4292(5), b = 29.772(1), c = 11.2989(5) Å, α = 91.152(3), β = 119.266(4), γ = 92.624(3)° and V = 3346.4(2) Å3. The refinement of an anisotropic model led to an R index of 0.0347 for 21,061 independent reflections. Thirty-two Sb sites, five S sites and 67 oxygen sites occur in the crystal structure of coquandite. Sb atoms display the characteristic SbO3 E and SbO4 E coordinations whereas S fills (SO4) tetrahedral groups. These atoms are arranged in five symmetry-independent layers perpendicular to b*. Four of them and their centrosymmetrical counterparts form complex modules stacked along b* and bonded through two Sb atoms and H bonds. The complex H bonding system in the structure is discussed. On the basis of information gained from this characterization, the crystal-chemical formula was revised according to the structural results, yielding Sb6+x O8+x (SO4)(OH)x ·(H2O)1–x (Z = 10) with x = 0.3 instead of Sb6O8(SO4)·H2O (Z = 12) as reported previously. A recalculation of the chemical data listed in the scientific literature for coquandite according to the structural results obtained here leads to a satisfactory agreement.