Relianceite-(K), K4Mg(V4+O)2(C2O4)(PO3OH)4(H2O)10, is a new mineral species from the Rowley mine, Maricopa County, Arizona, USA. It occurs in an unusual bat-guano-related, post-mining assemblage of phases. Other secondary minerals associated with relianceite-(K) are antipinite, dendoraite-(NH4), fluorite, mimetite, mottramite, rowleyite, salammoniac, struvite, vanadinite, willemite, wulfenite and at least one other new mineral. Crystals of relianceite-(K) are sky blue prisms up to ~0.1 mm in length. The streak is very pale blue and lustre is vitreous, Mohs hardness is 2½, tenacity is brittle and fracture is splintery. The calculated density is 2.111 g⋅cm–3. Relianceite-(K) is optically biaxial (+) with α = 1.528(2), β = 1.529(2), γ = 1.562(2) (white light); 2Vmeas = 22(1)°; orientation Z = b; pleochroism: X = colourless, Y = pale blue, Z = pale blue; X < Y ≈ Z. Electron microprobe analysis gave the empirical formula [K2.21(NH4)1.79]Σ4.00Mg0.96(V4+0.95O)2(C2O4)[P1.03O3.03(OH)0.97]4(H2O)10, with the C, N and H contents constrained by the crystal structure. Raman spectroscopy confirmed the presence of NH4 and C2O4. Relianceite-(K) is monoclinic, Pc, with a = 12.404 (7) Å, b = 9.014 (6), c = 13.260 (8) Å, β = 100.803(10)°, V = 1456 (2) Å3 and Z = 2. The structural unit in the crystal structure of relianceite-(K) (R1 = 0.0540 for 3751 Io > 2σI reflections) is a (V4+O)2(C2O4)(PO3OH)4 chain in which VO6 octahedra are bridged by an oxalate group to form [V2C2O12] dimers, PO3OH tetrahedra form a double bridge between the VO6 octahedra of the dimers, and additional PO3OH tetrahedra decorate the chain. Topologically, this is the same chain found in the structure of davidbrownite-(NH4). The MgO(H2O)5 octahedron can be considered a distant decoration on the chain. The chains are linked to each other through an extensive system of K/NH4–O bonds and hydrogen bonds.

For this study, the rare Cu-bearing silicate fumarolic assemblages from the Somma–Vesuvius volcano, Italy, characterised by the rare mineral litidionite, CuKNaSi4O10, were investigated. We report new data about Cu- and Ti-bearing phases found in these mineralisations, in which Ti-bearing litidionite occurs together with kamenevite, perovskite and rutile. Ti-bearing litidionite appears on the latest stages of partial crystallisation of Ti-bearing silica glass. Incorporation of Ti4+ into the litidionite crystal structure was investigated in detail. The Raman spectra of Ti-bearing litidionite contains an intense band at 597 cm−1 related to anti-symmetric bending vibrations of Si‒O bonds or overlapping stretching vibrations of Ti‒O bonds. The bands in the range 350‒500 cm−1 correspond to symmetric bending vibrations of O‒Si‒O bonds and overlapping stretching vibrations of Ti‒O bonds. The crystal structure of Ti-litidionite has been refined in the P$\bar{1}$ space group, a = 6.9699(7), b = 7.9953(10), c = 9.8227(10) Å, α = 105.186(9), β = 99.458(8) and γ = 114.489(10) to R1 = 0.064 for 1726 unique observed reflections. The refinement of the site-occupation factors confirmed the presence of Ti at a five-coordinated M site. The mean bond distance of 2.125 Å for the M site agrees with its refined occupancy (Ti0.32Cu0.30Ca0.29Fe0.09)1.00. The incorporation of Ti into the litidionite structure is accompanied by the complex heteropolyhedral substitution according to the scheme VTi4+ + VII–VIII□ + IVAl3+ ↔ VCu2+ + VII-VIII(Na,K)+ + IVSi4+. Two possible configurations for the phase with maximal TiO2 content (12.06 wt.% or 0.56 Ti apfu) CuTiK□Na2Si7AlO20 (Z = 1) or CuTiK2Na□Si7AlO20 (Z = 1) have been proposed.

Historical samples of branchite, described by the Tuscan naturalist Paolo Savi (1798–1871) at the end of the 1830s, were re-examined through single-crystal X-ray diffraction, showing their identity with hartite, C20H34, a hydrocarbon mineral described by Haidinger in 1841. The refined unit-cell parameters are a = 11.4116(7), b = 20.9688(12), c = 7.4100(4) Å, α = 93.947(2), β = 100.734(2), γ = 80.524(2)°, V = 1716.99(17) Å3 and Z = 4; space group P1. The crystal structure was solved and refined up to R1 = 0.0424 for 13512 reflections with Fo > 4σ(Fo) and 1265 refined parameters. As the name ‘branchite’ has priority over ‘hartite’, the reinstatement of the former name and the discreditation of the latter were approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA–CNMNC). Branchite is one of only eleven minerals formed by C and H listed in the official IMA List of Minerals. The type locality of branchite is the Botro di Lavajano, Monte Vaso, Chianni, Pisa, Tuscany, Italy. Neotype material is kept in the Natural History Museum of the Pisa University under catalogue number 14426.

Kainite, KMg(SO4)Cl⋅2.75H2O, is one of the most common hydrated sulfate minerals, and it plays an important role as a source of potassium. However, its properties and structure have, to date, been insufficiently studied. In our present work, kainite was investigated using multiple techniques, including single-crystal and powder X-ray diffraction, thermogravimetry, differential scanning calorimetry (DSC), and infrared spectroscopy (IR). The mineral is monoclinic, C2/m, a = 19.6742(2), b = 16.18240(10), c = 9.49140(10) Å, β = 94.8840(10)°, V = 3010.86(5) Å3 and Z = 16. The structure was refined to R1 = 0.0230 for 3080 unique observed reflections with |Fo| ≥ 4σF. The complex hydrogen bonding system for kainite is described for the first time. The structure of kainite contains seven symmetrically independent sites occupied by water molecules, six of which are strongly bonded to Mg2+ cations while the seventh resides in the framework cavities. The acceptors of the hydrogen bonds are either chloride anions, neighbouring water molecules or oxygens atoms of sulfate groups. A bifurcated hydrogen bond was described for one of the water molecules. Based on the analysis of the crystal structure, we have confirmed and propose the correct formula for kainite as KMg(SO4)Cl⋅2.75H2O. The thermal studies of kainite in the temperature range of –150°C to +600°C indicate its stability to 190°C. The decomposition products are K2Mg2(SO4)3, KCl and K2SO4. The thermal expansion was calculated, which for kainite has a character typical for monoclinic crystals and similar to the compressibility tensor described earlier.

A new occurrence of kintoreite, ideally PbFe3(PO4)(PO3OH)(OH)6, is described from the Tripi mine, Alì, Peloritani Mountains, northeastern Sicily, Italy. Kintoreite occurs as yellow equant crystals, up to 0.05 mm in size, on quartz, associated with another alunite-supergroup mineral currently under study. The studied grains of kintoreite are chemically zoned, showing the occurrence of two distinct domains. Electron microprobe analyses gave (in wt.%): SO3 5.47(27), P2O5 17.55(14), Al2O3 7.81(35), Fe2O3 23.81(44), PbO 35.11(41), H2Ocalc 9.93, total 99.68 (darker domains) and SO3 6.03(5), P2O5 16.66(23), Al2O3 4.22(2), Fe2O3 27.31(6), PbO 33.78(22), H2Ocalc 10.25, total 98.25 (brighter domains). On the basis of 14 O atoms per formula unit (apfu) and (P+S) = 2 apfu, the darker and brighter domains have chemical formula Pb1.00(Fe3+1.89Al0.97)Σ2.86[P1.57S0.43O7.43(OH)0.57][(OH)5.58(H2O)0.42]Σ6.00 and Pb0.98(Fe3+2.21Al0.53)Σ2.74[P1.51S0.49O7.49(OH)0.51][(OH)5.18(H2O)0.82]Σ6.00, respectively. Single-crystal X-ray diffraction was performed on a grain extracted from the same sample. Unit-cell parameters are a = 7.2191(10), c = 16.834(3) Å, V = 759.8(3) Å3 and Z = 3; space group R$\bar{3}$m. The crystal structure was refined on the basis of 226 unique reflections with Fo > 4σ(Fo) and 31 least-square parameters to R1 = 0.0415. Kintoreite is isotypic with other alunite-supergroup minerals. Micro-Raman spectroscopy suggests the possible occurrence of H2O groups, supporting the possible protonation of (OH) groups as a charge-balance mechanism in this mineral. Kintoreite may play an environmental role in the Alì area, where previous authors detected high concentrations of potentially toxic elements in soils.

The structure of corundum is not amenable to accommodating beryllium, yet Be is commonly added to corundum for purposes of colour modification. Where the main sites in corundum are octahedrally coordinated, Be is tetrahedrally coordinated in all known Be minerals. To attempt to explain this discrepancy, the configurations of Be in the Be–Al–O±H system were determined using density functional theory (DFT). In the Be–Al–O system, the most likely Be configuration is in triangular coordination, replacing Al and bonded to three oxygen on the basal plane (large triangle) of the Al-vacant octahedral site. When H is added, OH groups form at the opposite face of the same octahedron, pointing either into or out of the site. Be–H (beryllium hydride) defects are also stable at the DFT level, with Be bonded to three O and one H. As some defects contain O–H or Be–H bonds, the DFT calculations can be corroborated by FTIR spectroscopy. Spectra recorded from 1000 corundum crystals with elevated Be confirm that bands centred at 3062 and 2490 cm–1 correspond to Be-associated defects. Polarised spectra show that the band at 2490 cm–1 resolves into two, one centred at 2491 cm–1, with a shoulder at 2523 cm–1, one of which is probably associated with a Be–H bond. The 3062 cm–1 band resolves into at least three, including a major band at 3058 cm–1, a shoulder at 3140 cm–1 and a small, sharp band at 3082 cm–1. Whilst there are caveats relating to curve fitting and baseline subtraction, the 3058 cm–1 band can probably be attributed to the defect where H points into the Al-vacant octahedral site, and the 3140 cm–1 band to the defect where the H points out. To our knowledge, this is the first occurrence of Be in triangular coordination proposed for a naturally occurring mineral. This substitution mechanism may also explain the high diffusivity of Be, as Be is effectively associated with its own Al vacancy.

Svetlanaite, SnSe is a new mineral discovered from the high-sulfidation epithermal Au-deposit Ozernovskoe, Kamchatka peninsula, Russia. It forms tiny euhedral spindles (0.5–2 μm × 10–15 μm) in quartz, in close association with cassiterite, rutile, mohite, mawsonite, kiddcreekite, hemusite, tellurium, kostovite and Se-bearing ‘fahlores’ (Se-goldfieldite–Se(Bi)-tetrahedrite–Se-tennantite). In plane-polarised light, svetlanaite is light-grey, pleochroic from white to cream and strongly anisotropic in shades of light blue, dark blue, khaki and orange–brown; it exhibits no internal reflections. Reflectance values of synthetic analogue of svetlanaite in air (R1,R2 in %) are: 50.9, 56.5 at 470 nm, 50.2, 56.7 at 546 nm, 49.5, 55.3 at 589 nm and 48.7, 53.4 at 650 nm. Twelve electron-microprobe analyses of svetlanaite give an average composition: Sn 61.30, Se 37.22 and S 1.25 total 99.79 wt.%, corresponding to the empirical formula Sn1.01(Se0.92S0.07)Σ0.99 based on 2 atoms; the average of seven analyses on its synthetic analogue is: Sn 59.98 and Se 39.71, total 99.59 wt.%, corresponding to Sn1.00Se1.00. The density, calculated on the basis of the empirical formula, is 6.08 g/cm3. The mineral is orthorhombic, space group Pnma, with a = 11.500(2), b = 4.154(2), c = 4.445(2) Å, V = 212.34(14) Å3 and Z = 4. The crystal structure was solved and refined from the powder X-ray-diffraction data of synthetic SnSe. It crystallises in the GeS-structure type. It is isostructural with the mineral herzenbergite (SnS). The mineral name is in honour of Svetlana K. Smirnova, a Russian mineralogist, for her contributions to geology in the epithermal Au–Ag deposits of the Tien–Shan region.

Gurzhiite, ideally Al(UO2)(SO4)2F⋅10H2O, is a new uranyl sulfate mineral from the Bykogorskoe U deposit, Northern Caucasus, Russia. It occurs as fine-grained aggregates forming veinlets up to 50 cm long in cracks of the brecciated rock. Gurzhiite aggregates are composed of small bladed crystals up to 0.1 mm across. Associated minerals include khademite and quartz. Gurzhiite is pale yellow in crystals, lemon yellow in aggregates, transparent with a vitreous lustre and a white streak. It is brittle and has an irregular fracture. Cleavage is good on {001}. The new mineral exhibits a bright yellow–green fluorescence under both longwave and shortwave UV radiation. Mohs hardness is ~2. Dmeas = 2.52(3) g/cm3 and Dcalc = 2.605 g/cm3. The mineral is biaxial (–) with α = 1.528(3), β = 1.538(2), γ = 1.544(3) (589 nm); 2Vmeas= 80(10)° and 2Vcalc = 75.1°. The empirical formula calculated on the basis of 21(O + F) atoms per formula unit (apfu) is Al0.92Zn0.05Fe3+0.03Na0.03U0.95S2.00O9.85F0.99⋅10.16H2O. Gurzhiite is triclinic, with space group P$\bar{1}$, a = 7.193(2), b = 11.760(2), c = 11.792(2) Å, α = 67.20(3), β = 107.76(3), γ = 89.99(3)°, V = 867.7(4) Å3 and Z = 2. The five strongest lines of the powder X-ray diffraction pattern [d, Å (I, %)(hkl)] are: 10.24(100)(001); 5.40(14)($\bar{ 1}\bar{1}$1); 5.11(54)(002); 3.405(11)($\bar{2}$11); and 3.065(11)($\bar{1}\bar{1}$3). The crystal structure of gurzhiite is based upon uranyl sulfate chains of the same type as in bobcookite and svornostite. Between the chains are two types of Al-octahedra – Al1(H2O)6 and Al2F2(H2O)4. The entire structure stability is maintained by a complex network of H bonds. The new mineral honours Russian mineralogist and crystallographer Dr. Vladislav V. Gurzhiy in recognition for his contributions to uranium mineralogy and crystallography.

Following the identification of a new occurrence of melanostibite from the Apuan Alps, the crystal chemistry of this mineral has been re-examined using specimens from its type locality, Sjögruvan, Örebro County, Sweden, and from the new occurrence, the Scortico–Ravazzone Mn ore deposit, Apuan Alps, Tuscany, Italy. Both specimens were examined through electron microprobe analysis, micro-Raman spectroscopy and single-crystal X-ray diffraction data; Mössbauer spectroscopy was used for the Swedish specimen. Electron microprobe data indicate a close to ideal composition Mn2Fe3+Sb5+O6 for both samples, whereas Mössbauer spectroscopy confirmed the trivalent oxidation state of Fe. Single-crystal X-ray diffraction for the Swedish and Italian specimens points to the acentric nature of melanostibite, space group R3. Refined unit-cell parameters of melanostibite from Scortico–Ravazzone and Sjögruvan are a = 5.2351(3), c = 14.3645(8) Å, V = 340.93(4) Å3, and a = 5.2314(2), c = 14.3518(8) Å, V = 340.15(3) Å3, respectively. Melanostibite is an homeotypic derivative of pyrophanite.

The new sodalite-group mineral sapozhnikovite, ideally Na8(Al6Si6O24)(HS)2, was discovered in a hydrothermally altered urtite-like rock at Karnasurt Mountain, Lovozero alkaline massif, Kola Peninsula, Russia. The associated minerals are nepheline, aegirine, potassic feldspar, albite, kyanoxalite, natrolite, fluorapatite, fluorcaphite, lomonosovite (partially or completely altered to murmanite) and loparite-(Ce). Sapozhnikovite forms isolated colourless to pale greyish anhedral equant grains up to 5 mm across. The streak is white and the lustre is vitreous. Strong orange fluorescence under longwave UV radiation (λ = 330 nm) and weak yellow-orange fluorescence under shortwave UV radiation (λ = 245 nm) is observed. Sapozhnikovite is brittle, with a Mohs hardness of 5½. Cleavage is imperfect on (110). Density measured by flotation in heavy liquids is equal to 2.25(1) g⋅cm–3. The calculated density is 2.255 g⋅cm–3. Sapozhnikovite is characterised by infrared, Raman, electron spin resonance, NIR-Vis-UV absorption, and photoluminescence spectroscopy. The chemical composition is (wt.%, electron microprobe, H2O determined by gas chromatography of ignition products): Na2O 25.05, Al2O3 32.44, SiO2 37.58, HS 4.33, Cl 2.22, H2O 0.30, –O≡(Cl,HS) –1.55, total 100.37. The empirical formula is Na7.73Al6.08Si5.97O24(HS)1.25Cl0.60⋅0.16H2O. The crystal structure was determined using single-crystal X-ray diffraction data and refined to R1 = 1.62%. Sapozhnikovite is cubic, P$\bar{4}$3n, with a = 8.9146(1) Å, V = 708.45(2) Å3 and Z = 1. The new mineral is isostructural with sodalite. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 6.30 (37) (110), 3.638 (100) (211), 2.821 (14) (310), 2.572 (18) (222), 2.382 (16) (321) and 2.101 (29) (411). The mineral is named in honour of the Russian mineralogist and crystallographer Dr. Anatoly Nikolaevich Sapozhnikov (b. 1946).

Calciolangbeinite, ideally K2Ca2(SO4)3, exists in two modifications, cubic and, first described in the present paper, orthorhombic. They are topologically-similar polymorphs which can be designated as calciolangbeinite-C and calciolangbeinite-O. Calciolangbeinite-O is the first natural orthorhombic langbeinite-like sulfate. It clearly differs from calciolangbeinite-C in the powder X-ray diffraction pattern, optical data and Raman spectrum. Calciolangbeinite-O is found in sublimates of the active Arsenatnaya fumarole at the Tolbachik volcano, Kamchatka, Far Eastern Region, Russia and in pyrometamorphic rocks of the Hatrurim Complex at Jabel Harmun, Judean Desert, Palestinian Autonomy and Har Parsa, Negev Desert, both in Israel. Calciolangbeinite-C is known only in fumarole sublimates at Tolbachik. Calciolangbeinite forms a continuous solid-solution system with langbeinite K2Mg2(SO4)3. The majority of the system is represented by cubic phases, and only members with compositions K2(Ca2.0–1.9Mg0.0–0.1)(SO4)3 have orthorhombic symmetry under room-temperature conditions. The crystal structure of calciolangbeinite-O was studied on a single crystal, chemically very close to K2Ca2(SO4)3, from Tolbachik (R1 = 2.75%). The unit-cell parameters are: a = 10.3330(2), b = 10.5027(2), c = 10.1763(2) Å, V = 1104.37(4) Å3 and Z = 4; space group is P212121. Calciolangbeinite-O is a low-temperature modification of K2Ca2(SO4)3 belonging to the K2Cd2(SO4)3 structure type whereas calciolangbeinite-C (space group P213), a high-temperature modification, has the langbeinite-type structure. The significant Mg admixture in calciolangbeinite-C from Tolbachik probably stabilises its cubic structure at room temperature. In both high-temperature fumaroles and pyrometamorphic rocks calciolangbeinite crystallises in the cubic modification, and during cooling its chemical variety close to the end-member K2Ca2(SO4)3 undergoes phase transition to calciolangbeinite-O, whereas the Mg-enriched varieties of the mineral remain calciolangbeinite-C.

Scroll-like crystals of molybdenite, 2–5 mm in size, were found in phengite rock from the outer contact of the granular quartz vein of the Kyshtym quartz deposit. Platy and partly scrolled molybdenite occur in the same phengite rock from the outer contact of the quartz–feldspar pegmatite of the Slyudyanogorsk mica deposit. Both occurrences are located in the Ufaley metamorphic block in the South Urals. Scroll-like molybdenite crystals can associate with platy and partly twisted crystals in the same samples. The chemical composition of molybdenite was studied by inductively coupled plasma mass spectrometry (ICP-MS) and electron probe microanalysis (EPMA). Polytypes of molybdenite were identified with electron back-scattered diffraction (EBSD) and X-ray diffraction (XRD). Both scroll-like and platy molybdenite crystals are only represented by the 3R polytype, are enriched in Re up to 1 wt.% and contain no other significant impurities. Scroll-like molybdenite is twisted mainly around the crystallographic axis X. Twinning with a rotation of 60 degrees around the Z crystallographic axis is fixed in the plane (ab). The most probable origin of scroll molybdenites is the consequent growth of molybdenite around nucleation centres, which are commonly represented by mica crystals. The formation of the 3R polytype is caused by the difference in dimension of the layers enriched and depleted in rhenium.

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:

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

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.

Pyrope xenocrysts (N = 52) with associated inclusions of Ti- and/or Cr-rich oxide minerals from the Aldanskaya dyke and Ogonek diatreme (Chompolo field, southeastern Siberian craton) have been investigated. The majority of xenocrysts are of lherzolitic paragenesis and have concave-upwards (normal) rare earth element (REEN) patterns that increase in concentration from light REE to medium–heavy REE (Group 1). Four Ca-rich (5.7–7.4 wt.% CaO) pyropes are extremely low in Ti, Na and Y and have sinusoidal REEN spectra, thus exhibiting distinct geochemical signatures (Group 2). A peculiar xenocryst, s165, is the only sample to show harzburgitic derivation, whilst demonstrating a normal-to-weakly sinusoidal REEN pattern and the highest Zr (93 ppm) and Sc (471 ppm). Chromite–magnesiochromite, rutile, Mg-ilmenite and crichtonite-group minerals comprise a suite of oxide mineral inclusions in the pyrope xenocrysts. These minerals are characteristically enriched in Cr with 0.6–7.2 wt.% Cr2O3 in rutile, 0.7–3.6 wt.% in Mg-ilmenite and 7.1–18.0 wt.% in the crichtonite-group minerals. Complex titanates of the crichtonite group enriched in large ion lithophile elements (LILE) are high in Al2O3 (0.9–2.2 wt.%), ZrO2 (1.5–5.4 wt.%) and display a trend of compositions from the Ca–Sr-specific varieties to the Ba-dominant species (e.g. lindsleyite). In the pyrope xenocrysts the oxides coexist with silicates (clino- and orthopyroxene and olivine), hydrous silicates (talc, phlogopite and amphibole), carbonate (magnesite), sulfides (pentlandite, chalcopyrite, breakdown products of monosulfide and bornite solid solutions), apatite and graphite. P–T estimates imply the inclusion-bearing pyrope xenocrysts have been derived from low-temperature peridotite assemblages that resided at temperatures of ~600–800°C and a pressure range of ~25–35 kbar in the graphite stability field. Pyrope genesis is linked to the metasomatic enrichment of peridotite protoliths by Ca–Zr–LILE-bearing percolating fluid–melt phases containing significant volatile components. These metasomatic agents are probably volatile-rich melts or supercritical C–O–H–S fluids that were released from a Palaeo-subduction slab.

A recent review paper on nepheline solid solutions dealt mainly with sodic varieties from nepheline syenites and differentiated alkali basaltic sills. Excel spreadsheets were provided for recalculating cell formulae in terms of the stoichiometric parameters ΔAlcavity cation charge and ΔTframework charge and molecular percentages of the end-members Ne, Ks, Ca-nepheline and excess Si (Qxs). Small amounts of tetrahedral divalent species (usually <0.10 wt.% though with up to 0.33 wt.% MgO) were related to a stuffed-tridymite end-member of ideal formula K8Mg4Si12O32 (denoted KsT2+-nepheline), although the equations used to calculate these end-members only considered Si, Al and Fe3+ as tetrahedral framework species. Recently, K-rich nepheline and kalsilite which contain up 0.54 wt.% MgO have been found in some feldspar-free mafic potassic volcanic rocks from central Brazil. Equations have been developed to deal rigorously with the presence of significant amounts of Mg (and Mn) in recalculating nepheline solid-solution parameters. In two related communications reworked spreadsheets are provided with examples of their use. High quality microprobe analyses of nepheline and kalsilite from magmatic rocks must include analyses for Mg and Mn and, if possible, estimates of Fe2+ contents.

Barium melilite – bennesherite, Ba2Fe2+Si2O7, known only from pyrometamorphic rocks of the Hatrurim Complex in Israel, has been recognised in a carbonate–silicate xenolith from the Bellerberg volcano area in Germany. The empirical formula of the German specimen is as follows: (Ba1.32Ca0.43Sr0.23Na0.05K0.02)Σ2.05(Fe2+0.79Ti0.06Mg0.05Al0.04Mn0.03Zn0.01)Σ0.98Si1.97O7. The Raman spectrum of bennesherite exhibits the presence of the main vibrations related to Fe2+O4 tetrahedra and disilicate Si2O7 groups at the T1 and T2 sites, at 589 cm–1 and in the range 618–673 cm–1, respectively. Detailed spectroscopic analyses performed for bennesherite in two different and random orientations confirm the reduction of bands intensity and the number of some components in several spectral ranges. Moreover, the presence of a heavy Ba atom indicates a decrease in band frequencies compared to melilites with Ca at the X position. A single-crystal X-ray diffraction experiment, despite attempts, could not be carried out due to the poor quality and small size of the bennesherite crystals however, a combination of composition and Raman data allowed for accurate phase identification. Detailed mineralogical investigations distinguished rare Ba minerals in association with bennesherite, such as walstromite, fresnoite and celsian, along with various ferrous melilites. Some of the detected phases are described from xenoliths of the Bellerberg volcano for the first time. The uniqueness of the Bellerberg volcano mineralisation is reflected in the interaction of alkaline magma with xenoliths of different compositions, which suggests that this locality still deserves attention as a source of new and unique minerals.

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.

The new sodalite-group mineral bolotinaite, ideally (Na7□)(Al6Si6O24)F⋅4H2O, was discovered in a volcanic ejectum of trachitoid sanidinite collected from the In den Dellen (Zieglowski) pumice quarry, Laach Lake (Laacher See) palaeovolcano, Eifel region, Rhineland-Palatinate, Germany. The associated minerals are sanidine, nepheline, annite and zircon. Bolotinaite occurs as isolated interpenetration prismatic twins on (111) up to 1.3 mm long, complex twins, and rare non-twinned rhombic dodecahedra up to 0.2 mm across. The colour of bolotinaite is pale yellow to pinkish coloured, the streak is white and the lustre is vitreous. Weak orange–yellow fluorescence under longwave ultraviolet radiation (λ = 330 nm) is due to the presence of trace amounts of the S2•– radical anion. Bolotinaite is brittle, with a Mohs’ hardness of 5. No cleavage is observed. The fracture is uneven. D(meas) = 2.27(2) g⋅cm–3, D(calc) = 2.291 g⋅cm–3. Bolotinaite is optically isotropic, with n = 1.488(2) (λ = 589 nm). The chemical composition is (wt.%, electron microprobe, CO2 determined by quantitative IR spectroscopy analysis, H2O calculated from the empirical formula with four H2O molecules per formula unit): Na2O 18.30, K2O 3.87, CaO 0.57, Al2O3 28.85, SiO2 37.97, CO2 1.66, SO3 1.37, F 1.60, Cl 0.57, 2.22, H2O 7.21, –O≡(F,Cl) –0.80, total 101.17. The empirical formula is (Na5.92K0.82Ca0.10H0.08)(Si6.33Al5.67O24)(SO4)0.17F0.84Cl0.16(H2O)3.96(CO2)0.38. A high content of H2O and the presence of CO2 molecules and H+ cations as well as trace amounts of S2•– are confirmed by means of infrared and Raman spectroscopy. The crystal structure was determined using single-crystal X-ray diffraction data and refined to R = 0.0335. Bolotinaite is cubic, space group I$\bar{4}$3m, with a = 9.027(1) Å, V = 735.7(2) Å3 and Z = 1. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 6.36 (47) (110), 4.502 (10) (200), 3.679 (100) (211), 2.851 (28) (310), 2.603 (29) (222) and 2.126 (18) (330). The mineral is named in honour of the Russian crystallographer and crystal chemist Dr. Nadezhda Borisovna Bolotina (b. 1949).

Natural nepheline usually contains very small amounts of MgO (<0.1 wt.%), although these examples are mainly from Mg-poor alkaline igneous rocks such as nepheline syenites. However, this work shows that nepheline and kalsilite with much higher MgO concentrations can occur in the groundmass of strongly SiO2-undersaturated, feldspar-free, mafic volcanic rocks (i.e. olivine-rich foidites). Furthermore, a strong positive correlation is evident between their Mg and Fe contents. The occurrence of Mg-rich nepheline and kalsilite seems to be related to their derivation from Mg-rich magmas when compared to most of the host rocks investigated to date. Additionally, the physicochemical conditions of crystallisation seem to have an important role in the incorporation of ‘small’ divalent cations by these minerals. The prevalence of Mg-rich nepheline and kalsilite as late magmatic phases and the divergent Mg and Fe relationships for phenocrysts and ‘quenched’ groundmass crystals support this hypothesis. The positive correlation between Mg and Fe contents reflects their strong geochemical affinity and the entrance of Fe3+, Fe2+ and Mg2+ cations into the same crystallographic site of nepheline and kalsilite structures. The calculation of atomic formulae and stoichiometry parameters for nepheline-group minerals where data for the T2+ cations (e.g. Mg2+) are incorporated gives more reliable compositional parameters (see Paper 1). Calculated excess silica values (Si′) are affected significantly when the coupled substitution 2Al3+ = Mg2+ + Si4+ is considered. Thus, specific analyses of ‘small’ divalent cations are essential to obtain more realistic values of excess Si′, in particular, for nepheline and kalsilite that crystallised from Mg-rich, Si-poor, mafic–ultramafic alkaline lavas.