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The thermal behavior of 15 natural tourmaline samples has been measured by X-ray powder diffraction from room temperature to ~930 °C. Axial thermal expansion is generally greater along the c crystallographic axis (αc 0.90–1.05 × 10–5/K) than along the a crystallographic axis and the symmetrically equivalent b axis (αa 0.47–0.60 × 10–5/K). Ferro-bearing samples show lower expansion along a than in other tourmalines. In povondraite the thermal expansion along the c axis is higher than in other tourmalines, whereas along a it is lower [αa = 0.31(2) and αc = 1.49(3) × 10–5/K]. Volume expansion in the tourmaline-supergroup minerals is relatively low compared with other silicates such as pyroxenes and amphiboles. Volume also exhibits a relatively narrow range of thermal expansion coefficients (1.90–2.05 × 10–5/K) among the supergroup members. An interpretation for the small changes in thermal expansion in a compositionally heterogeneous group like tourmaline is that all members, except povondraite, share a framework of dominantly ZAlO6 polyhedra that limit thermal expansion. Povondraite, with a framework dominated by ZFe3+O6 polyhedra, displays thermal expansion that is different from other members of the group. Unit-cell dimensions of tourmalines having significant Fe2+ deviate from linearity above 400 °C on plots against temperature (T); along with the resulting substantial reduction in unit-cell volume, these effects are likely the result of deprotonation/oxidation processes. Lithium-rich and Fe2+-free tourmalines deviate similarly at T > 600 °C. In Li- and Fe2+-free tourmalines, no such deviation is observed up to the highest temperatures of our experiments. It is not clear whether this is due to cation order-disorder over Y and Z sites that occurs during the highest temperature measurements, a phenomenon that is apparently inhibited (at least in the short term) in Li-free/Mg-rich samples. If so, this must occur at a relatively rapid rate, as no difference in unit-cell values was detected at 800 °C after heating in both one- and 12-h experiments on Na-rich rossmanite.

New guidelines for the nomenclature of polymorphs and polysomes have been approved by the the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA–CNMNC). Several cases can be distinguished. (i) Polymorphs with different crystal systems are distinguished by the prefixes cubo- (cubic), hexa- (hexagonal), tetra- (tetragonal), trigo- (trigonal), ortho- (orthorhombic), clino- (monoclinic) and anortho- (triclinic). (ii) Polymorphs with different crystal systems but showing a pseudosymmetry should show the prefix ‘pseudo-’. (iii) Polymorphs with the same crystal system but different space groups are distinguished by the prefix ‘para-’. If three or more polymorphs show the same crystal system but different space groups, the space group notation may be added as a suffix, though such a nomenclature should be avoided if possible. (iv) Polymorphs with the same space group are distinguished by the prefix ‘para-’. (v) Minerals with polymorph suffixes but with different chemical compositions cannot be considered as true polymorphs, so we recommend using the prefix ‘meta-’, which indicates a close but significantly different chemical composition. (vi) Polysomatic symbols should be placed as a suffix, which indicates the number and types of modules that alternate in the structure, such as in the högbomite supergroup, or as prefixes as in the sartorite homologous series. These recommendations have to be applied for future new mineral proposals, when the authors decide to use structural prefixes or suffixes, however modifications of historical and well-established names have to pass through the CNMNC for approval. In order to be consistent with the new guidelines, 25 mineral names are now modified: domeykite-β becomes trigodomeykite; fergusonite-(Y)-β becomes clinofergusonite-(Y); fergusonite-(Ce)-β becomes clinofergusonite-(Ce); fergusonite-(Nd)-β becomes clinofergusonite-(Nd); ice-VII becomes cubo-ice; roselite-β becomes anorthoroselite; sulphur-β becomes clinosulphur; mertieite-II becomes mertieite; mertieite-I becomes pseudomertieite; uranophane-α becomes uranophane; uranophane-β becomes parauranophane; gersdorffite-P213 becomes gersdorffite; gersdorffite-Pa3 becomes paragersdorffite; gersdorffite-Pca21 becomes orthogersdorffite; betalomonosovite becomes paralomonosovite; lammerite-β becomes paralammerite; nováčekite-I becomes hydronováčekite; nováčekite-II becomes nováčekite; halloysite-7Å becomes halloysite; halloysite-10Å becomes hydrohalloysite; metauranocircite-I becomes metauranocircite; taimyrite-I becomes taimyrite; uranocircite-II becomes uranocircite; andorite IV becomes quatrandorite; and andorite VI becomes senandorite.

The new tourmaline supergroup mineral dutrowite, Na(Fe2.52+Ti0.5)Al6(Si6O18)(BO3)3(OH)3O, has been discovered in an outcrop of a Permian metarhyolite near the hamlet of Fornovolasco, Apuan Alps, Tuscany, Italy. It occurs as chemically homogeneous domains, up to 0.5 mm, brown in colour, with a light-brown streak and a vitreous lustre, within anhedral to subhedral prismatic crystals, up to 1 mm in size, closely associated with Fe-rich oxy-dravite. Dutrowite is trigonal, space group R3m, with a=15.9864(8), c=7.2187(4) Å, V=1597.68(18) Å3, and Z=3. The crystal structure was refined to R1=0.0257 for 1095 unique reflections with Fo>4σ (Fo) and 94 refined parameters. Electron microprobe analysis, coupled with Mössbauer spectroscopy, resulted in the empirical structural formula X(Na0.81Ca0.20K0.01)Σ1.02 Y(Fe1.252+Mg0.76Ti0.56Al0.42)Σ3.00 Z(Al4.71Fe0.273+V0.023+Mg0.82Fe0.182+)Σ6.00 T[(Si5.82Al0.18)Σ6.00O18] (BO3)3O(3)(OH)3O(1)[O0.59(OH)0.41]Σ1.00, which was recast in the empirical ordered formula, required for classification purposes: X(Na0.81Ca0.20K0.01)Σ1.02 Y(Fe1.432+Mg1.00Ti0.56)Σ3.00 Z(Al5.13Fe0.273+V0.023+Mg0.58)Σ6.00 T[(Si5.82Al0.18)Σ6.00O18] (BO3)3V(OH)3 W[O0.59(OH)0.41]Σ1.00. Dutrowite is an oxy-species belonging to the alkali group of the tourmaline supergroup. Titanium is hosted in octahedral coordination, and its incorporation is probably due to the substitution 2Al3+ = Ti4+ + (Fe,Mg)2+. Its occurrence seems to be related to late-stage high-T/low-P replacement of “biotite” during the late-magmatic/hydrothermal evolution of the Permian metarhyolite.

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).

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}}$$ Uvite is a hydroxy-species belonging to the calcic-group of the tourmaline supergroup. The closest end-member compositions of valid tourmaline species are fluor-uvite and feruvite, to which uvite is related by the substitutions W(OH)– ↔ WF– and YMg2+ ↔ YFe2+, respectively. The occurrence of a solid-solution between uvite and magnesio-lucchesiite, according to the substitution ZMg2+ + W(OH)– ↔ ZAl3+ + WO2–, is supported by experimental data. The new mineral was approved by the IMA–CNMNC (IMA 2019-113). Uvite from Facciatoia formed by the reaction between B-rich fluids, released during the crystallisation process of LCT pegmatites, and the surrounding metaserpentinites, altered by contact metamorphism in the aureole of the Miocene Mt. Capanne monzogranitic pluton.

Lombardoite, ideally Ba2Mn3+(AsO4)2(OH), and aldomarinoite, ideally Sr2Mn3+(AsO4)2(OH), are two new minerals of the arsenbrackebuschite group in the brackebuschite supergroup, discovered in Fe–Mn ore in metaquartzites of the abandoned mine of Valletta, Canosio, Val Maira, Cuneo Province, Piedmont, Italy. They occur as red–brown and orange brown, respectively, as subhedral crystals (< 0.5 mm) in thin masses, associated with quartz, aegirine, baryte, calcite, hematite, muscovite and Mn minerals such as cryptomelane, braunite and manganberzeliite. Both minerals are translucent, have yellow–orange streak and vitreous lustre. Both are brittle. Estimated Mohs hardness is 6–6½ for lombardoite (by analogy to canosioite), and 4½–5 for aldomarinoite (by analogy to tokyoite). Calculated densities are 5.124 g/cm3 for lombardoite and 4.679 g/cm3 for aldomarinoite. Both minerals are biaxial (+). Lombardoite shows 2Vz(meas.) = 78(4)° and is pleochroic with X = yellowish brown, Y = brown and Z = reddish brown (Z > Y > X). Aldomarinoite has 2Vz(meas.) = 67.1(1)°, and is pleochroic with X = brown, Y = brownish orange and Z = yellowish brown (Z > Y > X). Point analyses by electron microprobe using wavelength dispersive spectroscopy resulted in the empirical formula (based on 9 O anions): (Ba1.96Sr0.17Pb0.04Na0.02Ca0.02)Σ2.21(Mn3+0.62Fe3+0.13Al0.06Mg0.11)Σ0.92[(As0.87V0.12P0.01)Σ1.00O4]2(OH) for lombardoite, and (Sr1.93Ca0.21Ba0.04Pb0.01)Σ2.19(Mn3+0.48Al0.35Fe3+0.21Mg0.01)Σ1.05[(As0.92V0.03)Σ0.95O4]2(OH) for aldomarinoite. The absence of H2O was confirmed by Raman spectroscopy and infrared spectroscopy. Both minerals are monoclinic, P21/m, with unit-cell parameters a = 7.8636(1) Å, b = 6.13418(1) Å, c = 9.1197(1) Å, β = 112.660(2)° and V = 405.94(1) Å3, for lombardoite and a = 7.5577(4) Å, b = 5.9978(3) Å, c = 8.7387(4) Å, β = 111.938(6)° and V = 367.43(3) Å3, for aldomarinoite. The eight strongest powder X-ray diffraction lines are [d, Å (Irel) (hkl)]: 6.985 (39) (10$\bar{1}$), 3.727 (33) (111), 3.314 (100) (21$\bar{1}$), 3.073 (24) (020), 3.036 (33) (21$\bar{2}$, 10$\bar{3}$), 2.810 (87) (12$\bar{1}$, 112), 2.125 (20) (301, 11$\bar{4}$) and 1.748 (24) (321) for lombardoite and 3.191 (89) (21$\bar{1}$), 2.997 (45) (020), 2.914 (47) (21$\bar{2}$, 10$\bar{3}$), 2.715 (100) (112), 2.087 (39) (12$\bar{3}$, 1.833 (32) (31$\bar{4}$), 1.689 (36) (321), 1.664 (21) (132) for aldomarinoite. The minerals are isostructural with brackebuschite: infinite chains of edge sharing octahedra running parallel to the b axis and decorated with AsO4 groups are connected along the a and c axes through Ba and Sr atoms in lombardoite and aldomarinoite, respectively. The minerals are named after Bruno Lombardo (1944–2014), geologist and petrologist at C.N.R. (National Research Council of Italy), and Aldo Marino (b. 1942) the mineral collector and founding member of the AMI – Italian Micromineralogical Association.

Celleriite, ☐(Mn22+Al)Al6(Si6O18)(BO3)3(OH)3(OH), is a new mineral of the tourmaline supergroup. It was discovered in the Rosina pegmatite, San Piero in Campo, Elba Island, Italy (holotype specimen), and in the Pikárec pegmatite, western Moravia, Czech Republic (co-type specimen). Celleriite in hand specimen is violet to gray-blue (holotype) and dark brownish-green (co-type) with a vitreous luster, conchoidal fracture, and white streak. Celleriite has a Mohs hardness of ~7 and a calculated density of 3.13 and 3.14 g/cm3 for holotype and its co-type, respectively. In plane-polarized light in thin section, celleriite is pleochroic (O = pale violet and E = light gray-blue in holotype; O = pale green and E = colorless in co-type) and uniaxial negative. Celleriite has trigonal symmetry: space group R3m, Z = 3, a = 15.9518(4) and 15.9332(3) Å, c = 7.1579(2) and 7.13086(15) Å, V = 1577.38(9) and 1567.76(6) Å3 for holotype and co-type, respectively (data from single-crystal X-ray diffraction). The crystal structure of the holotype specimen was refined to R1 = 2.89% using 1696 unique reflections collected with MoKα X-ray intensity data. Structural, chemical, and spectroscopic analyses resulted in the formulas: x ( ◻ 0.58 N a 0.42 ) Σ 1.00 Y ( M n 1.39 2 + F e 0.16 2 + M g 0.01 A l 1.14 F e 0.01 3 + L i 0.28 T i 0.01 ) Σ 3.00 Z A l 6 [ T ( S i 5.99 A l 0.01 ) Σ 6.00 O 18 ] ( B O 3 ) 3 ( O H ) 3 w [ ( O H ) 0.65 F 0.03 O 0.32 ] Σ 1.00 ( for holotype ) and x ( ◻ 0.51 N a 0.49 ) Σ 1.00 Y ( M n 0.90 2 + F e 0.50 2 + A l 1.36 F e 0.04 3 + L i 0.17 Zn 0.04 ) Σ 3.00 Z A l 6 [ T ( S i 5.75 B 0.25 ) Σ 6.00 O 18 ] ( B O 3 ) 3 ( O H ) 3 w [ ( O H ) 0.35 F 0.17 O 0.48 ] Σ 1.00 ( for co-type ) Celleriite is a hydroxy species belonging to the X-site vacant group of the tourmaline supergroup. The new mineral was approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association, proposal no. 2019-089. In the Rosina pegmatite, celleriite formed an overgrowth at the analogous pole of elbaite–fluorelbaite–rossmanite crystals during the latest stage of evolution of pegmatite cavities after an event of a pocket rupture. In the Pikárec pegmatite, celleriite occurs as an intermediate growth sector of elbaite, princivalleite, and fluor-elbaite.

Piccoliite, ideally NaCaMn3+2(AsO4)2O(OH), is a new mineral discovered in the Fe–Mn ore hosted in metaquartzites of the Montaldo di Mondovì mine, Corsaglia Valley, Cuneo Province, Piedmont, Italy. It occurs as small and rare black crystals and aggregates hosted by a matrix of quartz, associated with calcite and berzeliite/manganberzeliite. It has been also found in the Valletta mine near Canosio, Maira Valley, Cuneo Province, Piedmont, Italy, where it occurs embedded in quartz associated with grandaite, hematite, tilasite/adelite and rarely thorianite. The mineral is opaque (thin splinters may be very dark red), with brown streak and has a resinous to vitreous lustre. It is brittle with irregular fracture. No cleavage has been observed. The measured Mohs hardness is ~5–5.5. Piccoliite is non fluorescent. The calculated density is 4.08 g⋅cm–3. Chemical spot analyses by electron microprobe analysis using wavelength dispersive spectroscopy resulted in the empirical formula (based on 10 anions per formula unit) (Na0.64Ca0.35)Σ0.99(Ca0.75Na0.24)Σ0.99(Mn3+1.08Fe3+0.59Mg0.20Ca0.10)Σ1.97(As2.03V0.03Si0.01)Σ2.07O9(OH) and (Na0.53Ca0.47)Σ1.00(Ca0.76Na0.23Sr0.01)Σ1.00(Mn3+0.63Fe3+0.49Mg0.48Mn4+0.34Ca0.06)Σ2.00(As1.97P0.01Si0.01)Σ1.99O9(OH) for the Montaldo di Mondovì and Valletta samples, respectively. The mineral is orthorhombic, Pbcm, with single-crystal unit-cell parameters a = 8.8761(9), b = 7.5190(8), c = 11.689(1) Å and V = 780.1(1) Å3 (Montaldo di Mondovì sample) and a = 8.8889(2), b = 7.5269(1), c = 11.6795(2) Å, V = 781.43(2) Å3 (Valletta sample) with Z = 4. The seven strongest powder X-ray diffraction lines for the sample from Montaldo di Mondovì are [d Å (Irel; hkl)]: 4.85 (57; 102), 3.470 (59; 120, 113), 3.167 (100; 022), 2.742 (30; 310, 213), 2.683 (53; 311, 023), 2.580 (50; 222, 114) and 2.325 (19; 320, 214, 223). The crystal structure (R1 = 0.0250 for 1554 unique reflections for the Montaldo di Mondovì sample and 0.0260 for 3242 unique reflections for the Valletta sample) has MnO5(OH) octahedra forming edge-shared dimers; these dimers are connected through corner-sharing, forming two-up-two-down [[6]M2([4]TO4)4φ2] chains [M = Mn; T = As; φ = O(OH)] running along [001]. These chains are bonded in the a and b directions by sharing corners with AsO4 tetrahedra, giving rise to a framework of tetrahedra and octahedra hosting seven-coordinated Ca2+ and Na+ cations. The crystal structure of piccoliite is closely related to that of pilawite-(Y) as well as to carminite-group minerals that also show the same type of chains but with different linkage. The mineral is named after the mineral collectors Gian Paolo Piccoli and Gian Carlo Piccoli (father and son) (1926–1996 and b. 1953, respectively), the latter having discovered the type material at the Montaldo di Mondovì mine.

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).

This study aims to solve the site-occupancy issues of any crystalline substance, showing that the structure refinement results should not be limited to a simple description of the crystal geometry but should go beyond that, providing refined site-scattering values consistent with the chemical data., A detailed description of the structure of the amphibole-supergroup minerals is very challenging owing to their complex chemical composition that renders the process of cation partition extremely difficult, particularly because of the occurrence of multivalent elements. Since amphiboles naturally occur under a fibrous morphology and have largely been used to produce asbestos, there is a growing demand for detailed and accurate structural data in order to study the relationships between structure, composition and toxicity. The present study proposes a recommended refinement procedure for both X-ray single-crystal structure refinement (SREF) and Rietveld analysis for tremolite, selected as a test case. The corresponding structural results are compared to estimate the ‘degree of confidence’ of the Rietveld refinement with regard to SREF. In particular, it is shown that the interpretation of the electron density of the tremolite structure by SREF is model dependent. By assuming that the site-scattering values from SREF should be as close as possible to those from electron microprobe analysis, as a crucial constraint for the correct description of the final crystal-chemical model, it is found that it is best satisfied by using partially ionized scattering curves (SCs) for O and Si, and neutral SCs (neutral oxygen curves or NOCs) for other atoms. This combination leads to the best fit to the diffraction data. Moreover, it is found that Rietveld refinement using NOCs produces the best structural results, in excellent agreement with SREF. It is worth noting that, due to the complexity of the diffraction pattern and the fairly large number of freely refinable parameters, refinements with different combinations of SCs produce results almost indistinguishable from a statistical point of view, albeit showing significant differences from a structural point of view.

Magnesio-lucchesiite, ideally CaMg3Al6(Si6O18)(BO3)3(OH)3O, is a new mineral species of the tourmaline supergroup. The holotype material was discovered within a lamprophyre dike that cross-cuts tourmaline-rich metapelites within the exocontact of the O’Grady Batholith, Northwest Territories (Canada). Two additional samples were found at San Piero in Campo, Elba Island, Tuscany (Italy) in hydrothermal veins embedded in meta-serpentinites within the contact aureole of the Monte Capanne intrusion. The studied crystals of magnesio-lucchesiite are black in a hand sample with vitreous luster, conchoidal fracture, an estimated hardness of 7–8, and a calculated density of 3.168 (Canada) and 3.175 g/cm3 (Italy). In plane-polarized light, magnesio-lucchesiite is pleochroic (O = dark brown, E = colorless) and uniaxial (–); its refractive index values are nω = 1.668(3) and nε = 1.644(3) (Canada), and nω = 1.665(5) and nε = 1.645(5) (Italy). Magnesio-lucchesiite is trigonal, space group R3m, Z = 3, with a = 15.9910(3) Å, c = 7.2224(2) Å, V = 1599.42(7) Å3 (Canada) and with a = 15.9270(10) Å, c = 7.1270(5) Å, V = 1565.7(2) Å3 (Italy, sample 1). The crystal structure of magnesio-lucchesiite was refined to R1 = 3.06% using 2953 reflections with Fo > 4σ(Fo) (Canadian sample; 1.96% / 1225 for the Italian sample) The Canadian (holotype) sample has the ordered empirical formula X(Ca0.60Na0.39K0.01)Σ1.00Y(Mg2.02Fe0.622+Fe0.093+Ti0.25V0.01Cr0.01)Σ3.00Z(Al5.31Fe0.693+)Σ6.00[T(Si5.98Al0.02)Σ6.00O18](BO3)3V[(OH)2.59O0.41]Σ3.00W(O0.78F0.22)Σ1.00. The Italian (co-type) material shows a wider chemical variability, with two different samples from the same locality having ordered chemical formulas: X(Ca0.88Na0.12)Σ1.00Y(Mg1.45Fe0.402+Al0.79Fe0.363+)Σ3.00ZAl6[T(Si5.05Al0.95)Σ6.00O18](BO3)3V[(OH)2.90O0.10]Σ3.00W(O0.98F0.02)Σ1.00 (sample 1) and X(Ca0.71Na0.21☐0.08)Σ1.00Y(Mg2.49Fe0.412+Ti0.10)Σ3.00Z(Al5.44Fe0.463+Mg0.09V0.01)Σ6.00[T(Si5.87Al0.13)Σ6.00O18](BO3)3V(OH)3W[O0.61(OH)0.39]Σ1.00 (sample 2). Magnesio-lucchesiite is an oxy-species belonging to the calcic group of the tourmaline supergroup. It is related to lucchesiite by the homovalent substitution YFe ↔ YMg, and to feruvite by the homovalent and heterovalent substitutions YFe ↔ YMg and ZAl3+ + WO2– ↔ ZMg2+ + W(OH)1–. The new mineral was approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA 2019-025). Occurrences of magnesio-lucchesiite show that its presence is not restricted to replacement of mafic minerals only; it may also form in metacarbonate rocks by fluctuations of F and Al during crystallization of common uvitic tourmaline. High miscibility with other tourmaline end-members indicates the large petrogenetic potential of magnesio-lucchesiite in Mg, Al-rich calc-silicate rocks, as well as contact-metamorphic and metasomatic rocks.

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’.

Table S1: Luinaite-(OH): sites, fractional atomic coordinates, isotropic (*) or equivalent-isotropic displacement parameters (in Å2), site occupancies (s.o.) for schorl-1A from Cleveland tin mine, Australia (Sample LUI-AUS), and for oxy-dravite-1A from Blue Mountain Saddle, USA (Sample LUI-USA); Table S2: Luinaite-(OH): selected bond distances (in Å) for schorl-1A from Cleveland tin mine, Australia (Sample LUI-AUS), and for oxy-dravite-1A from Blue Mountain Saddle, USA (Sample LUI-USA); Crystallographic Information Files: LUI-AUS.cif and LUI-USA.cif.

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.

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 formulaX(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.

Mineral species should be identified by an end-member formula and by using the dominant-valency rule as recommended by the IMA–CNMNC. However, the dominant-end-member approach has also been used in the literature. These two approaches generally converge, but for some intermediate compositions, significant differences between the dominant-valency rule and the dominant end-member approach can be observed. As demonstrated for garnet-supergroup minerals, for example, the end-member approach is ambiguous, as end-member proportions strongly depend on the calculation sequence. For this reason, the IMA–CNMNC strongly recommends the use of the dominant-valency rule for mineral nomenclature, because it alone may lead to unambiguous mineral identification. Although the simple application of the dominant-valency rule is successful for the identification of many mineral compositions, sometimes it leads to unbalanced end-member formulae, due to the occurrence of a coupled heterovalent substitution at two sites along with a heterovalent substitution at a single site. In these cases, it may be useful to use the site-total-charge approach to identify the dominant root-charge arrangement on which to apply the dominant-constituent rule. The dominant-valency rule and the site-total-charge approach may be considered two procedures complementary to each other for mineral identification. Their critical point is to find the most appropriate root-charge and atomic arrangements consistent with the overriding condition dictated by the end-member formula. These procedures were approved by the IMA−CNMNC in May 2019.

A crystal chemical investigation of a natural specimen of whitlockite, ideally Ca9Mg(PO4)6[PO3(OH)], from Palermo Mine (USA), was achieved by means of a combination of electron microprobe analysis (EMPA) in WDS mode, single-crystal neutron diffraction probe (NDP) and single-crystal X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy. The crystal-chemical characterization resulted in the empirical formula (Ca8.682Na0.274Sr0.045)Σ9.000(Ca0.034□0.996)Σ1.000(Mg0.533Fe2+0.342Mn2+0.062Al0.046)Σ0.983(P1.006O4)6[PO3(OH0.968F0.032)Σ1.000]. Crystal-structure refinement, in the space group R3c, converged to R1 = 7.12% using 3273 unique reflections from NDP data and to R1 = 2.43% using 2687 unique reflections from XRD data. Unit cell parameters from NDP are a = 10.357(3) Å, c = 37.095(15) Å and V = 3446(2) Å3, and from XRD, the parameters are a = 10.3685(4) Å, c = 37.1444(13) Å and V = 3458.2(3) Å3. NDP results allowed a deeper definition of the hydrogen-bond system and its relation with the structural unit [PO3(OH)]. The FTIR spectrum is very similar to that of synthetic tricalcium phosphate Ca3(PO4)2 and displays minor band shifts due to slightly different P-O bond lengths and to the presence of additional elements in the structure. A comparison between whitlockite, isotypic phases from the largest merrillite group, and its synthetic counterpart Ca3(PO4)2 is provided, based on the XRD/NDP and FTIR results.

The thermal behaviour of a fluor-elbaite from Minas Gerais (Brazil) was investigated at room pressure through in situ high-temperature X-ray powder diffraction (HT-XRPD), until the breakdown conditions were reached. The variations of fluor-elbaite structural parameters (unit-cell parameters and mean bond distances) were monitored together with site occupancies, and two main internal reactions were identified: the thermally-induced Fe oxidation process counterbalanced by (OH)– deprotonation, which starts at 500 °C (773 K), followed by a partial intracrystalline Fe–Al exchange between the octahedrally-coordinated Y and Z sites. The fluor-elbaite breakdown reaction occurs between 850 °C (1123 K) and 900 °C (1173 K). The breakdown products were identified at room temperature by XRPD and the breakdown reaction can be described by the following reaction: tourmaline → B-bearing mullite + hematite + spinel + B-poor (Na, Li, H2O)-bearing glass. Boromullite itself was not observed in the final heating products, and the B-bearing mullite from the breakdown reaction exhibited unit-cell parameters a = 7.5382(2) Å, b = 7.6749(2) Å, c = 2.8385(1) Å, V = 164.22(1) Å3 (space group Pbam) consistent with an approximate Al8.5B1.5Si2O19 composition.

The new mineral isselite, Cu6(SO4)(OH)10(H2O)4⋅H2O, has been discovered in the Lagoscuro mine, Monte Ramazzo mining complex, Genoa, Eastern Liguria, Italy. It occurs as sprays of blue acicular crystals, up to 0.1 mm long, associated with brochantite and posnjakite. Streak is light blue and the lustre is vitreous. Isselite is brittle, with irregular fracture and good cleavage on {001} and {100}. Measured density is 3.00(2) g/cm3. Isselite is optically biaxial (–), with α = 1.599(2), β = 1.633(2) and γ = 1.647(2) (determined in white light). The measured 2V is 63.6(5)°. Dispersion is moderate, withr>v. The optical orientation isX=b,Y=candZ=a. Isselite is pleochroic, withX= light blue,Y= blue,Z= blue;X< 4σ(Fo). It shows a layered structure formed by zig-zag {001} layers of Cu-centred polyhedra. Sulfate groups occur in the interlayer along with one H2O group. Isselite is chemically related to redgillite and montetrisaite.

The classification of the tetrahedrite group minerals in keeping with the current IMA-accepted nomenclature rules is discussed. Tetrahedrite isotypes are cubic, with space group symmetry I43m. The general structural formula of minerals belonging to this group can be written as M(2)A6M(1)(B4C2)X(3) D4S(1)Y12S(2)Z, where A = Cu+, Ag+, ☐ (vacancy), and (Ag6)4+ clusters; B = Cu+, and Ag+; C = Zn2+, Fe2+, Hg2+, Cd2+, Mn2+, Cu2+, Cu+, and Fe3+; D = Sb3+, As3+, Bi3+, and Te4+; Y = S2– and Se2–; and Z = S 2–, Se2–, and ☐. The occurrence of both Me+ and Me2+ cations at the M(1) site, in a 4:2 atomic ratio, is a case of valency-imposed double site-occupancy. Consequently, different combinations of B and C constituents should be regarded as separate mineral species. The tetrahedrite group is divided into five different series on the basis of the A, B, D, and Y constituents, i.e., the tetrahedrite, tennantite, freibergite, hakite, and giraudite series. The nature of the dominant C constituent (the so-called “charge-compensating constituent”) is made explicit using a hyphenated suffix between parentheses. Rozhdestvenskayaite, arsenofreibergite, and goldfieldite could be the names of three other series. Eleven minerals belonging to the tetrahedrite group are considered as valid species: argentotennantite-(Zn), argentotetrahedrite-(Fe), kenoargentotetrahedrite-(Fe), giraudite-(Zn), goldfieldite, hakite-(Hg), rozhdestvenskayaite-(Zn), tennantite-(Fe), tennantite-(Zn), tetrahedrite-(Fe), and tetrahedrite-(Zn). Furthermore, annivite is formally discredited. Minerals corresponding to different end-member compositions should be approved as new mineral species by the IMA-CNMNC following the submission of regular proposals. The nomenclature and classification system of the tetrahedrite group, approved by the IMA-CNMNC, allows the full description of the chemical variability of the tetrahedrite minerals and it is able to convey important chemical information not only to mineralogists but also to ore geologists and industry professionals.

Twenty natural spinel single crystals displaying colors almost representative for the entire spinel variability were investigated by electron microprobe and UV–VIS–NIR–MIR and FTIR spectroscopies. Eight of them, selected among the Fe-bearing ones, were also analyzed by X-ray diffraction, and five by Mossbauer spectroscopy to obtain information on the oxidation state and site distribution of Fe. The adopted multi-analytical approach was successful in revealing that the color displayed by aluminate spinel crystals is due to a combination of two or more minor transition elements acting as chromophore, such as V3+, Cr3+, Fe2+, Fe3+, Mn2+ and Mn3+, variably distributed in the tetrahedrally and octahedrally coordinated sites of the spinel structure. Iron-poor orange, red and magenta spinel crystals owe their color mainly to the presence of V3+ and Cr3+ at the M sites (with predominance of V3+ for orange and of Cr3+ for red color). Iron-rich pink, blue and green spinel crystals, in spite of exhibiting very different colors, have relatively similar optical absorption spectra characterized by a strong UV-edge absorption and a series of weak absorption bands in the visible range. From pink to blue and green spinel samples, color differences depend on the increase of Fetot (primarily) and Fe3+ contents (secondarily), which are responsible for both the intensification of UV-edge absorption and the different intensity, width and position of the prominent absorption bands occurring in the range 18,000−15,000 cm−1. The scarcity in nature of yellow spinel is explained by the rarity of conditions necessary to obtain the yellow color, such as the exclusive presence of Mn acting as a chromophore or at least the absence of Fe2+, to avoid masking of the weak electronic transitions in Fe3+, Mn2+ and Mn3+.

Tourmalines from the late-Variscan Arbus pluton (SW Sardinia) and its metamorphic aureole were structurally and chemically characterized by single-crystal X-ray diffraction, electron and nuclear microprobe analysis, Mossbauer, infrared and optical absorption spectroscopy, to elucidate their origin and relationships with the magmatic evolution during the pluton cooling stages. The Arbus pluton represents a peculiar shallow magmatic system, characterized by sekaninaite (Fe-cordierite)-bearing peraluminous granitoids, linked via AFC processes to gabbroic mantle-derived magmas. The Fe2+-Al-dominant tourmalines occur in: a) pegmatitic layers and pods, as prismatic crystals; b) greisenized rocks and spotted granophyric dikes, as clots or nests of fine-grained crystals in small miaroles locally forming orbicules; c) pegmatitic veins and pods close to the contacts within the metamorphic aureole. Structural formulae indicate that tourmaline in pegmatitic layers is schorl, whereas in greisenized rocks it ranges from schorl to fluor-schorl. Tourmalines in thermometamorphosed contact aureole are schorl, foitite and Mg-rich oxy-schorl. The main substitution is Na + Fe2+ ↔ □ + Al, which relates schorl to foitite. The homovalent substitution (OH) ↔ F at the O1 crystallographic site relates schorl to fluor-schorl, while the heterovalent substitution Fe2+ + (OH, F) ↔ Al + O relates schorl/fluor-schorl to oxy-schorl. Tourmaline crystallization in the Arbus pluton was promoted by volatile (B, F and H2O) enrichment, low oxygen fugacity and Fe2+ activity. The mineralogical evolutive trend is driven by decreasing temperature, as follows: sekaninaite + quartz → schorl + quartz → fluor-schorl + quartz → foitite + quartz. The schorl → foitite evolution represents a distinct trend towards (Al + □) increase and unit-cell volume decrease. These trends are typical of granitic magmas and consistent with Li-poor granitic melts, as supported by the absence of elbaite and other Li-minerals in the Arbus pluton. Tourmaline-bearing rocks reflect the petrogenetic significance of contribution from a metapelitic crustal component during the evolution of magmas in the middle-upper crust.

Oxy-foitite, □(Fe 2+ Al 2 )Al 6 (Si 6 O 18 )(BO 3 ) 3 (OH) 3 O, is a new mineral of the tourmaline supergroup. It occurs in high-grade migmatitic gneisses of pelitic composition at the Cooma metamorphic Complex (New South Wales, Australia), in association with muscovite, K-feldspar and quartz. Crystals are black with a vitreous luster, sub-conchoidal fracture and gray streak. Oxy-foitite has a Mohs hardness of ∼7, and has a calculated density of 3.143 g/cm 3 . In plane-polarized light, oxy-foitite is pleochroic ( O = dark brown and E = pale brown), uniaxial negative. Oxy-foitite belongs to the trigonal crystal system, space group R 3 m , a = 15.9387(3) A, c = 7.1507(1) A and V = 1573.20(6) A 3 , Z = 3. The crystal structure of oxy-foitite was refined to R 1 = 1.48% using 3247 unique reflections from single-crystal X-ray diffraction using Mo K α radiation. Crystal-chemical analysis resulted in the empirical structural formula: X ( □ 0.53 Na 0.45 Ca 0.01 K 0.01 ) ∑ 1.00 Y ( Al 1.53 Fe 2 + 1.16 Mg 0.22 Mn 2 + 0.05 Zn 0.01 Ti 4 + 0.03 ) ∑ 3.00 Z ( Al 5.47 Fe 3 + 0.14 Mg 0.39 ) ∑ 6.00 [ ( Si 5.89 Al 0.11 ) ∑ 6.00 O 18 ] ( BO 3 ) 3 V ( OH ) 3 W [ O 0.57 F 0.04 ( OH ) 0.39 ] ∑ 1.00 . Oxy-foitite belongs to the X -site vacant group of the tourmaline-supergroup minerals, and shows chemical relationships with foitite through the substitution Y Al 3+ + W O 2− → Y Fe 2+ + W (OH) 1− .

Four specimens of the roméite-group minerals oxyplumboroméite and fluorcalcioroméite from the Långban Mn-Fe deposit in Central Sweden were structurally and chemically characterized by single-crystal X-ray diffraction, electron microprobe analysis and infrared spectroscopy. The data obtained and those on additional roméite samples from literature show that the main structural variations within the roméite group are related to variations in the content of Pb2+, which is incorporated into the roméite structure via the substitution Pb2+→A2+ where A2+ = Ca, Mn and Sr. Additionally, the cation occupancy at the six-fold coordinated B site, which is associated with the heterovalent substitution BFe3+ + Y☐→BSb5++YO2-, can strongly affect structural parameters.Chemical formulae of the roméite minerals group are discussed. According to crystal-chemical information, the species associated with the name ‘kenoplumboroméite’, hydroxycalcioroméite and fluorcalcioroméite most closely approximate end-member compositions Pb2(SbFe3+)O6☐, Ca2(Sb5+Ti) O6(OH) and (CaNa)Sb2O6F, respectively. However, in accord with pyrochlore nomenclature rules, their names correspond to multiple end-members and are best described by the general formulae: (Pb,#)2(Sb,#)2O6☐, (Ca,#)2(Sb,#)2O6(OH) and (Ca,#)Sb2(O,#)6F, where ‘#’ indicates an unspecified charge-balancing chemical substituent, including vacancies.

The crystal structure of turneaureite, ideally Ca 5 (AsO 4 ) 3 Cl, was studied using a specimen from the Brattfors mine, Nordmark, Varmland, Sweden, by means of single-crystal X-ray diffraction data. The structure was refined to R 1 = 0.017 on the basis of 716 unique reflections with F o > 4σ( F o ) in the P 6 3 / m space group, with unit-cell parameters a = 9.9218(3), c = 6.8638(2) A, V = 585.16(4) A 3 . The chemical composition of the sample, determined by electron-microprobe analysis, is (in wt%; average of 10 spot analyses): SO 3 0.22, P 2 O 5 0.20, V 2 O 5 0.01, As 2 O 5 51.76, SiO 2 0.06, CaO 41.39, MnO 1.89, SrO 0.12, BaO 0.52, PbO 0.10, Na 2 O 0.02, F 0.32, Cl 2.56, H 2 O calc 0.58, O(≡F+Cl) −0.71, total 99.04. On the basis of 13 anions per formula unit, the empirical formula corresponds to (Ca 4.82 Mn 0.17 Ba 0.02 Sr 0.01 ) ∑ 5.02 (As 2.94 P 0.02 S 0.02 Si 0.01 ) ∑ 2.99 O 12 [Cl 0.47 (OH) 0.42 F 0.11 ] ∑ 1.00 . Turneaureite is topologically similar to the other members of the apatite supergroup: columns of face-sharing M 1 polyhedra running along c are connected through T O 4 tetrahedra with channels hosting M 2 cations and X anions. Owing to its particular chemical composition, the studied turneaureite can be considered as a ternary calcium arsenate apatite; consequently it has several partially filled anion sites within the anion columns. Polarized single-crystal FTIR spectra of the studied sample indicate stronger hydrogen bonding and less diverse short-range atom arrangements around (OH) groups in turneaureite as compared to the related minerals johnbaumite and svabite. An accurate knowledge of the atomic arrangement of this apatite-remediation mineral represents an improvement in our understanding of minerals able to sequester and stabilize heavy metals such as arsenic in polluted areas.

Crystal-chemical relations and classification problems in tourmalines belonging to the oxy-schorl—oxy-dravite—bosiite—povondraite series

Lucchesiite, CaFe32+Al6(Si6O18)(BO3)3(OH)3O, is a new mineral of the tourmaline supergroup. It occurs in the Ratnapura District, Sri Lanka (6°35'N, 80°35'E), most probably from pegmatites and in Mirošov near Strážek, western Moravia, Czech Republic, (49°27'49.38"N, 16°9'54.34"E) in anatectic pegmatite contaminated by host calc-silicate rock. Crystals are black with a vitreous lustre, conchoidal fracture and grey streak. Lucchesiite has a Mohs hardnessof ∼7 and a calculated density of 3.209 g/cm3(Sri Lanka) to 3.243 g/cm3(Czech Republic). In plane-polarized light, lucchesiite is pleochroic (O = very dark brown and E = light brown) and uniaxial (–). Lucchesiite is rhombohedral, space groupR3m,a≈ 16.00 Å,c≈ 7.21 Å,V≈ 1599.9 Å3,Z= 3. The crystal structure of lucchesiite was refined toR1 ≈ 1.5% using ∼2000 unique reflections collected with MoKα X-ray intensity data. Crystal-chemical analysis for the Sri Lanka (holotype) and Czech Republic (cotype) samples resulted in the empirical formulae, respectively:X(Ca0.69Na0.30K0.02)∑1.01Y(Fe1.442+Mg0.72Al0.48Ti0.334+V0.023+Mn0.013+Zn0.01)∑3.00Z(Al4.74Mg1.01Fe0.253+)∑6.00[T(Si5.85Al0.15)∑6.00O18](BO3)3V(OH)3W[O0.69F0.24(OH)0.07]∑1.00andX(Ca0.49Na0.45□0.05K0.01)∑1.00Y(Fe1.142+Fe0.953+Mg0.42Al0.37Mn0.03Ti0.084+Zn0.01)∑3.00Z(Al5.11Fe0.383+Mg0.52)∑6.00[T(Si5.88Al0.12)∑6.00O18](BO3)3V[(OH)2.66O0.34]∑3.00W(O0.94F0.06)∑1.00.Lucchesiite is an oxy-species belonging to the calcic group of the tourmaline supergroup. The closest end-member composition of a valid tourmaline species is that of feruvite, to which lucchesiite is ideally related by the heterovalent coupled substitutionZAl3++O1O2–↔ZMg2++O1(OH)1–. The new mineral was approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA 2015-043).

Flux-grown spinel crystals belonging to the MgAl 2 O 4 -MgCr 2 O 4 spinel series were investigated to reveal the effects of Cr substituting for Al on cation distribution and their influence on Mg-Al intra-crystalline exchange. Samples were structurally and chemically characterized by single-crystal X-ray diffraction and electron microprobe, and cation distribution was obtained with a tested optimization model for site populations. The results evidenced that the contribution of the tetrahedral bond distance to the unit-cell parameter is smaller than that of the octahedral bond distance, which is driven by the substitution of Cr for Al. Moreover, the influence that Cr exerts on Mg-Al order-disorder intersite exchange is non-linear along the whole series. The comparison between the cation distributions derived from crystal-chemical data and the O’Neill-Navrotsky thermodynamic model (with α Mg-Al = 23 kJ/mol and β Mg-Al = 13 kJ/mol) shows large discrepancies, which can be reconciled assuming α Mg-Al values variable from 23 to 100 kJ/mol as a function of Cr. This suggests that, irrespective of temperature, the Al ordering at the octahedrally coordinated site increases with increasing Cr substitution for Al. The geothermometric implications of the present study point out that closure temperatures, calculated from a well-tested intersite geothermometer, are reliable for spinels with magnesiochromite component smaller than 85%, i.e., Cr/(Cr+Al)

To univocally identify mineral species on the basis of their formula, the IMA-CNMNC recommends the use of the dominant-valency rule and/or the site-total-charge approach, which can be considered two procedures complementary to each other for mineral identification. In this regard, several worked examples are provided in this study along with some simple suggestions for a more consistent terminology and a straightforward use of mineral formulae. IMA-CNMNC guidelines subordinate the mineral structure to the mineral chemistry in the hierarchical scheme adopted for classification. Indeed, a contradiction appears when we first classify mineral species to form classes (based on their chemistry) and subsequently we group together them to form supergroups (based on their structure topology): To date, more than half of recognized mineral supergroups include species with different anions or anionic complexes. This observation is in contrast to the current use of chemical composition as the distinguishing factor at the highest level of mineral classification.

An inclusive study of tourmaline, a well-known petrogenetic indicator, allowed the reconstruction of late-stage evolution of B-bearing Variscan granodioritic magmas in Sardinia batholith (Italy). Tourmaline samples from Mandrolisai igneous massif were chemically and structurally investigated by electron microprobe analysis, single-crystal X-ray diffraction, Mossbauer, infrared and optical absorption spectroscopy. Tourmaline aggregates occur both as large crystals displaying graphic textures with quartz, in aplite layers and pegmatite dykes within tonalitic granodiorite, and as fine-grained assemblages, in tourmalinite veins crystallized along fractures within metamorphic country rocks. Tourmaline was identified as schorl in pegmatites and as dravite in veins, both with relevant foitite and magnesio-foitite components. Petrological and mineralogical constraints based on mineral oxythermobarometry and tourmaline crystal chemistry converged towards crystallization temperatures in the range 650–400 °C at about 2.2 kbar, under NNO conditions that remained almost unvaried during the whole magma crystallization path. In the reconstructed scenario, Mandrolisai tourmaline recorded the late stages of consolidation of a single granodioritic magma batch, whose crystallization path locally led to residual concentration of B in the melt. Due to melt/hydrous fluid immiscibility processes, B enrichment promoted the crystallization of the large tourmaline + quartz assemblages in pegmatites. Late B-bearing fluids triggered metasomatic reactions and favored the precipitation of fine-grained tourmaline in tourmalinite veins under a brittle solid-state regime, which overprinted a fracture network of the country rocks previously formed under magmatic flow conditions. Mandrolisai granodiorites are metaluminous (ASI = 0.93–0.95), that is far from the compositional characters of typical B-bearing magmas, mostly felsic and markedly peraluminous (ASI > 1.2). The uncommon occurrence of tourmaline-bearing rocks in Mandrolisai may be an evidence of the limited control exerted by Al2O3 saturation on the origin of tourmaline. Conversely, a more important role of B contents, likely coming from crustal sources, may be invoked for tourmaline saturation in the magma.

The empirical relations between cubic spinel oxides of different compositions were investigated using data from 349 refined crystal structures. The results show that the spinel structure is able to tolerate many constituents (at least 36) by enlarging and decreasing the tetrahedra and octahedra. This is reflected in a large variation in tetrahedral and octahedral bond distances. The oxygen positional parameter (u) may be regarded as a measure of the distortion of the spinel structure from cubic close packing or of the angular distortion of the octahedron. The distortion can best be explained in terms of ionic potential (IP), which merges the size and charge properties of an ion. Sterically induced distortion depends on ion size, whereas electrostatically induced distortion is caused by cation–cation repulsion across faces of tetrahedra and shared edges of octahedra. The strong correlations between theuparameter and the IP at theTandMsites are consistent with the main role played by the both charge and size. Large distortions (u≫ 0.27) result in oxygen–oxygen distances of the octahedron shorter than 2.50 Å, which would lead to structural instability because of increased non-bonded repulsion forces between the oxygen atoms.

Hydroxylhedyphane, Ca2Pb3(AsO4)3(OH), a new member of the apatite supergroup from Langban, Sweden

Minerals in cement chemistry: A single-crystal neutron diffraction study of ettringite. Ca6Al2(SO4)3(OH)12.27H2O

An Fe-rich fluor-elbaite was thermally treated in air and hydrogen atmosphere up to 800 °C to study potential changes in Fe- and Al-ordering over the octahedrally coordinated Y and Z sites. Overall, the experimental data (structural refinement, electron and ion microprobe, Mossbauer, infrared and optical absorption spectroscopy) show that thermal treatment of fluor-elbaite results in an increase of Fe contents at the Z site balanced by an increase of Al at the Y site. On the basis of this and previous experimental studies on Fe–Mg–Al-bearing tourmalines, it can be stated that the intersite Fe–Mg–Al exchange rates are significant at temperatures around 700–800 °C. Thermal treatment results in an increase of ca. 0.30 Fe atoms per formula unit at the Z site compensated by a similar increase of (Mg + Al) at the Y site, following the exchange reaction YFe + Z(Mg + Al) → ZFe + Y(Mg + Al). Since the tourmaline nomenclature is based on the occupancy of ions at each structural site, the intersite Fe–Mg–Al ordering may determine the tourmaline species. This means that effectively the name associated with a given composition may be a function of the sample thermal history.

A dravite from Yemen of near end-member composition was treated in air and hydrogen atmospheres at 600–900 °C to reveal changes in Mg and Al order over the octahedrally coordinated Y and Z sites, and to explore related changes in the characteristic vibrational bands in the principal (OH)-stretching frequency. Relevant information was obtained using electron microprobe analysis (EMPA), structural refinement (SREF) and polarized infrared (IR) single-crystal spectroscopy. Overall, the EMPA, SREF and IR data show that only minor changes occur during thermal treatment up to at least 800 °C, including variations in structural parameters, Mg–Al order–disorder and (OH)-stretching bands, indicating limited hydrogen loss. Untreated and treated dravite samples have very similar long-range and short-range atomic structures, which may be related to the occurrence of stable Al–Mg extended clusters around the O1 (=W) and O3 (=V) sites: W(F)–Y(MgMgMg)–V(OH)3–Z[AlAlAlAlAl(Al,Mg)]; W(OH)–Y(MgMgAl)–V(OH)3–Z[AlAlAlAlAl(Al,Mg)]; W(O2–)–Y(AlAlAl)–V(OH)3–Z[AlAlAlAlAl(Al,Mg)]. These extended clusters remain stable to temperatures close to the observed start of decomposition (~900 °C).

Eight spinel single-crystal samples belonging to the spinel sensu stricto-magnesiocoulsonite series (MgAl2O4-MgV2O4) were synthesized and crystal-chemically characterized by X-ray diffraction, electron microprobe and optical absorption spectroscopy. Site populations show that the tetrahedrally coordinated site (T) is populated by Mg and minor Al for the spinel sensu stricto compositions, and only by Mg for the magnesiocoulsonite compositions, while the octahedrally coordinated site (M) is populated by Al, V3+, minor Mg, and very minor amounts of V4+. The latter occurs in appreciable amounts in the Al-free magnesium vanadate spinel, T(Mg)M(Mg0.26V3+1.48V4+0.26)O4, showing the presence of the inverse spinel VMg2O4. The studied samples are characterized by substitution of Al3+ for V3+ and (Mg2++V4+) for 2V3+ described in the system MgAl2O4-MgV2O4-VMg2O4. The present data in conjunction with data from the literature provide a basis for quantitative analyses of two solid-solution series MgAl2O4-MgV23+O4 and MgV23+O4-V4+Mg2O4. Unit-cell parameter increases with increasing V3+ along the series MgAl2O4-MgV2O4 (8.085–8.432 A), but only slightly increases with increasing V3+ along the series VMg2O4-MgV2O4 (8.386–8.432 A). Although a solid solution could be expected between the MgAl2O4 and VMg2O4 end-members, no evidence was found. Amounts of V4+ are nearly insignificant in all synthetic Al-bearing vanadate spinels, but are appreciable in Al-free vanadate spinel. An interesting observation of the present study is that despite the observed complete solid-solution along the MgAl2O4-MgV2O4 and MgV2O4-VMg2O4 series, the spinel structure seems to be unable to stabilize V4+ in any intermediate members on the MgAl2O4-Mg2VO4 join even at high oxygen fugacities. This behavior indicates that the accommodation of specific V-valences can be strongly influenced by crystal-structural constraints, and any evaluation of oxygen fugacities during mineral formation based exclusively on V cation valence distributions in spinel should be treated with caution. The present study underlines that the V valency distribution in spinels is not exclusively reflecting oxygen fugacities, but also depends on activities and solubilities of all chemical components in the crystallization environment.

We study the effects of cation inversion x (Mg ↔ Al, with x representing the fraction of Mg and Al exchanged) and magnetic substitution (Mn → Mg) on the elastic properties of the MgAl 2O 4 spinel system using density functional theory and Brillouin scattering techniques. Our computations show that cation inversion decreases the molar volume of spinel and produces a stiffening of C 11 and a softening of C 12. Simulations and experiments agree within 2 %. Density functional theory also captures the qualitative effect of Mg ↔ Al on C 44, that is, an initial softening for inversion degree at x < 0.125 and stiffening at x = 1, with a disagreement of