Thermessaite-(NH4), ideally (NH4)2AlF3(SO4), is a new mineral found as a medium- to high-temperature (~250–300°C) fumarole encrustation at the rim of La Fossa crater, Vulcano, Aeolian Islands, Italy. The mineral deposited as aggregates of minute (<0.2 mm) sharp prismatic crystals on the surface of a pyroclastic breccia in association with thermessaite, sulfur, arcanite, mascagnite, and intermediate members of the arcanite–mascagnite series.

The new mineral is colourless to white, transparent, non-fluorescent, has a vitreous lustre, and a white streak. The calculated density is 2.185 g/cm3. Thermessaite-(NH4) is orthorhombic, space group Pbcn, with a = 11.3005(3) Å, b = 8.6125(3) Å, c = 6.8501(2) Å, V = 666.69(4) Å3 and Z = 4. The eight strongest reflections in the powder X-ray diffraction data [d in Å (I)(hkl)] are: 5.65 (100)(200), 4.84 (89)(111), 6.85 (74)(110), 3.06 (56)(112), 3.06 (53)(221), 3.08 (47)(311), 2.68 (28)(022) and 2.78 (26)(130). The average chemical composition, determined by quantitative SEM-EDS (N by difference), is (wt.%): K2O 3.38, Al2O3 25.35, SO3 36.58, F 26.12, (NH4)2O 22.47, O = F –11.00, total 102.90. The empirical chemical formula, calculated on the basis of 7 anions per formula unit, is [(NH4)1.85K0.15]Σ2.00Al1.06F2.94S0.98O3.06. The crystal structure, determined from single-crystal X-ray diffraction data [R(F) = 0.0367], is characterised by corner-sharing AlF4O2 octahedra which form [001] octahedral chains by sharing two trans fluoride atoms [Al–F2 = 1.8394(6) Å]. Non-bridging Al–F1 distances are shorter [1.756(1) Å]. The two trans oxygen atoms [Al–O = 1.920(2) Å] are from SO4 tetrahedra. NH4+ ions occur in layers parallel to (100) which alternate regularly with (100) layers containing ribbons of corner-sharing AlF4O2 octahedra and associated SO4 groups. The NH4+ ions are surrounded by five oxygen atoms and by four fluorine atoms. The mineral is named as the (NH4)-analogue of thermessaite, K2AlF3(SO4), and corresponds to an anthropogenic phase found in the burning Anna I coal dump of the Anna mine, Aachen, Germany. Both mineral and mineral name have been approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA2011-077).

Cotype material of stibiogoldfieldite from the Mohawk mine, Goldfield, Nevada, USA, has been examined in order to collect single-crystal X-ray diffraction data of Te-rich stibiogoldfieldite and to characterise the associated Ag–Bi–(S,Se) phase. Tellurium-rich stibiogoldfieldite, with empirical formula (Cu11.30Ag0.03)Σ11.33(Sb0.80As0.57Bi0.06Te2.57)Σ4.00(S12.83Se0.20)Σ13.03, is cubic, space group I$\bar{4}$3m, with unit-cell parameters a = 10.2947(3) Å and V = 1091.04(10) Å3. Its crystal structure has been refined to R1 = 0.0161 for 397 unique reflections with Fo > 4σ(Fo) and 25 refined parameters. The structure refinement confirmed the occurrence of a vacancy at the M(2) site, in agreement with the substitution M(2)Cu+ + X(3)(Sb/As)3+ = M(2)□ + X(3)Te4+. The Ag–Bi–(S,Se) phase was identified as the 6P homologue of the pavonite series, namely dantopaite. Its empirical formula is Cu1.36Ag4.39Pb0.12Bi12.62Sb0.06(S14.01Se7.91Te0.08), showing an exceptionally high Se content. Unit-cell parameters of Se-bearing dantopaite are a = 13.518(2), b = 4.0898(6), c = 18.984(3) Å, β = 106.816(6)°, V = 1004.7(3) Å3 and space group C2/m. The crystal structure was refined to R1 = 0.0504 for 1230 unique reflections with Fo > 4σ(Fo) and 82 refined parameters. The metal excess (~0.55 atoms per formula unit) of this pavonite homologue is mainly due to the accumulation of Ag and Cu in the thin slab of the crystal structure, whereas the high Se content is related to the partial replacement of S occurring preferentially in the thick PbS-like slab. Domains richer in Se and Pb in dantopaite, with empirical formula Cu0.89Ag4.50Pb0.49Bi12.53Sb0.07(S11.26Se10.74), were also identified, as grains up to 30 μm in size intimately intergrown with bohdanowiczite, indicating the possibility of a wide Se-to-S substitution in dantopaite.

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

The new mineral bakakinite, ideally Ca2V2O7, was found in the high-temperature (not lower than 500°C) exhalations of the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with anhydrite, svabite, pliniusite, schäferite, berzeliite, diopside, hematite, powellite, baryte, fluorapatite, calciojohillerite, ludwigite, magnesioferrite, anorthite, titanite and esseneite. Bakakinite forms flattened crystals up to 30 × 5 μm, typically distorted. The mineral is transparent, colourless or pale yellow, with strong vitreous lustre. Electron microprobe analysis gave (wt.%): CaO 37.04, SrO 0.26, SiO2 0.16, P2O5 1.48, V2O5 49.47, As2O5 10.85, SO3 0.35, total 99.61. The empirical formula calculated on the basis of 7 O apfu is (Ca1.99Sr0.01)Σ2.00(V1.64As0.28P0.06Si0.01S0.01)Σ2.00O7. The Dcalc is 3.463 g cm–3. Bakakinite is triclinic, P$\bar{1}$, unit-cell parameters are: a = 6.64(2), b = 6.92(2), c = 7.01(2) Å, α = 86.59(7), β = 63.77(7), γ = 83.47(6)°, V = 287.0(5) Å3 and Z = 2. The strongest reflections of the powder X-ray diffraction pattern [d,Å(I)(hkl)] are: 4.647(27)(111, 0$\bar{1}$1), 3.138(76)(002), 3.103(100)(120, 121), 3.027(20)(021), 2.960(81)(200), 2.158(19)(031, 302), 1.791(16)(320), 1.682(16)(114) and 1.584(17)(1$\bar{3}$3, 403). Bakakinite is a natural analogue of synthetic Ca2V2O7. The mineral is named in honour of the outstanding Russian crystallographer and crystal chemist Vladimir Vasilievich Bakakin (born 1933).

The new mineral axelite, ideally Na14Cu7(AsO4)8F2Cl2, was found in the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with sylvite, halite, arsmirandite, bradaczekite, johillerite, tilasite, ericlaxmanite, lammerite, hematite, tenorite, cassiterite, pseudobrookite, aphthitalite-group sulfates, anhydrite, fluoborite, sanidine and fluorophlogopite. Axelite occurs as tabular, quadratic, rectangular or stronger distorted crystals up to 0.02 × 0.1 × 0.1 mm, sometimes combined in interrupted crusts up to 0.4 mm across overgrowing sylvite. It is transparent, sky-blue, with vitreous lustre. Cleavage was not observed. Dcalc is 3.662 g cm–3. Axelite is optically uniaxial (–), ɛ = 1.650(4) and ω = 1.678(4). Chemical composition (wt.%, electron microprobe data) is: Na2O 22.54, K2O 0.08, CaO 0.04, MgO 0.05, CuO 26.69, P2O5 1.75, V2O5 0.15, As2O5 44.14, SO3 0.04, F 1.57, Cl 3.60, –O=(F,Cl) –1.47, total 99.18. The empirical formula based on O+F+Cl=36 apfu is Na14.37K0.03Ca0.01Mg0.02Cu6.63P0.49V0.03As7.59S0.01O32.36F1.63Cl2.01. Axelite is tetragonal, P4bm, a = 14.5957(2), c = 8.34370(18) Å, V = 1777.51(6) Å3 and Z = 2. The strongest reflections of the powder X-ray diffraction (XRD) pattern [d,Å(I)(hkl)] are: 8.32(44)(001), 5.156(47)(220), 4.168(21)(002), 3.246(34)(222), 3.180(61)(331), 2.747(100)(402), 2.709(36)(511) and 2.580(29)(440). The crystal structure, solved from single-crystal XRD data (R = 4.50%), is unique. It is based on the heteropolyhedral chains built by clusters formed by CuO4Cl square pyramids connected with AsO4 tetrahedra. Adjacent chains are connected via common vertices of AsO4 tetrahedra with CuO4Cl pyramids to form a heteropolyhedral pseudo-framework. Axelite is remotely related, in both structural and chemical aspects, to lavendulan-like minerals and synthetic compounds. The mineral is named in honour of the outstanding Finnish–Russian crystallographer, mineralogist and material scientist Axel Gadolin (1828–1892).

A new mineral cuprodobrovolskyite, ideally Na4Cu(SO4)3, was found in sublimates of the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with petrovite, saranchinaite, euchlorine, krasheninnikovite, langbeinite, calciolangbeinite, anhydrite, sanidine, tenorite and hematite. Cuprodobrovolskyite occurs as coarse hexagonal tabular or equant, typically skeletal crystals up to 1 mm and their clusters or crusts up to 1.5 cm × 2.5 cm in area. The mineral is transparent, light blue or greenish-bluish to almost colourless with vitreous lustre. Cuprodobrovolskyite is optically uniaxial (+) with ω = 1.509(3) and ε = 1.528(3). The empirical formula calculated on the basis of 12 O apfu is (Na3.64K0.09Pb0.03)Σ3.76(Cu0.51Ca0.22Mg0.16Zn0.07Al0.01Mn0.01)Σ0.98S3.04O12. The unit-cell parameters of cuprodobrovolskyite calculated from the powder X-ray diffraction data are: a = 15.702(2), c = 22.017(5) Å, V = 4701.0(2) Å3, space group R3 and Z = 18. The crystal structure was studied using the Rietveld method, Rp = 0.0246, Rwp = 0.0325, R1 = 0.0521 and wR2 = 0.0770. Cuprodobrovolskyite is an isostructural analogue of dobrovolskyite Na4Ca(SO4)3 with Cu prevailing over Ca. One of the main features of cuprodobrovolskyite is Cu2+ in 7-fold coordination. On the basis of relationships with saranchinaite Na2Cu(SO4)2 and petrovite Na12Cu2(SO4)8 in the Arsenatnaya fumarole and the results of heating experiments, cuprodobrovolskyite is considered as the highest-temperature phase among anhydrous Na–Cu sulfate minerals.