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.

The new mineral evseevite was found in the Arsenatnaya fumarole, Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. Evseevite is represented by two chemical varieties. The variety close to the end-member Na2Mg(AsO4)F (holotype) is associated with sanidine, hematite, tenorite, aegirine, cassiterite, sylvite, halite, johillerite, badalovite, calciojohillerite, hatertite, arsmirandite, yurmarinite, axelite, polyarsite, aphthitalite, potassic-magnesio-fluoro-arfvedsonite, litidionite, ferrisanidine and tridymite. The P- and S-enriched variety (cotype) is associated with hematite, fluorophlogopite, svabite, fluorapatite, tilasite, calciojohillerite, forsterite, cassiterite, belomarinaite and aphthitalite. Evseevite occurs as prismatic, acicular or hair-like crystals up to 0.7 mm long combined in clusters up to 0.5 mm, brushes or crusts up to 2 × 2 mm. It is transparent, colourless or pale pinkish, with vitreous lustre. Dcalc is 3.377 g cm–3 for the holotype and 3.226 g cm–3 for the cotype. Evseevite is optically uniaxial (+), α = 1.545(2), β = 1.546(2), γ = 1.549(2) and 2Vmeas = 40(10)°. The empirical formulae calculated based on O+F = 5 apfu are (Na1.99Ca0.03K0.01)Σ2.03(Mg0.98Fe3+0.01Zn0.01Cu0.01)Σ1.01[(As0.98Si0.01)Σ1.01O4](F0.97O0.03) for the holotype and Na2.02(Mg1.00Fe3+0.03)Σ1.03[(As0.69P0.25S0.07)Σ1.01O4](F0.78O0.22) for the cotype. Evseevite is orthorhombic, Pbcn, a = 5.3224(1), b = 14.1255(3), c = 12.0047(3) Å, V = 902.53(4) Å3 and Z = 8. Strong reflections of the powder XRD pattern [d,Å(I)(hkl)] are: 4.001(100)(121), 3.479(56)(023), 3.041(45)(042), 2.657(44)(200), 2.642(68)(142) and 2.613(36)(104). The crystal structure was solved from single-crystal XRD data and refined on powder data by the Rietveld method, Rwp = 0.0068, Rp = 0.0047 and Robs = 0.0435. Evseevite is isostructural to moraskoite Na2Mg(PO4)F. The structure of evseevite can be described in terms of anion-centred polyhedra. F-centred octahedra [FNa4Mg2]7+ share faces to form chains [FNa2Mg]3+ and AsO4 tetrahedra are located between the chains. Evseevite belongs to a small set of minerals with antiperovskite structures and is the first natural arsenate with antiperovskite units. The mineral is named in honour of the Russian mineralogist Aleksandr Andreevich Evseev (born 1949).

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).

A new mineral kalithallite, K3Tl3+Cl6⋅2H2O, was found in an active fumarole belonging to the Northern fumarole field at the First scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. Kalithallite is a product of the relatively low-temperature (70–150°C) interactions involving high-temperature sublimate minerals, volcanic gas and atmospheric water vapour. The associated minerals are cryobostryxite, KZnCl3⋅2H2O, halite, sylvite, opal and gypsum. Kalithallite forms lamellar to tabular crystals up to 5 × 30 × 40 μm combined in open-work aggregates up to 1 mm across. It is transparent, colourless in individuals and white to pale cream coloured or pale beige in aggregates, with vitreous lustre. Dcalc = 3.01 g cm–3. Kalithallite is optically uniaxial (–), ɛ = 1.656(3) and ω = 1.662(3). The chemical composition (wt.%, electron-microprobe data, H2O calculated by stoichiometry) is: K 17.72, Zn 0.85, Tl 38.76, Cl 35.91, H2Ocalc 5.99, total 99.23. The empirical formula calculated on the basis of K+Zn+Tl+Cl = 10 apfu is K2.72Zn0.06Tl1.14Cl6.08⋅2H2O. Kalithallite is tetragonal, I4/mmm, a = 15.9333(5), c = 18.1088(7) Å, V = 4595.2(4) Å3 and Z = 14. The strongest reflections of the powder X-ray diffraction (XRD) pattern [d,Å(I)(hkl)] are: 5.98(100)(202); 5.64(36)(220); 3.984(20)(400); 3.528(30)(224); 3.315(22)(422); 2.890(15)(334); and 2.817(24)(206, 440). Kalithallite is isotypical to synthetic K3Tl3+Cl6⋅2H2O. The crystal structure was refined from the powder XRD data using the Rietveld method, RBragg = 0.55%, Rp = 0.56%, and Rwp = 0.75%. The structure contains Tl3+Cl6 octahedra and K-centred polyhedra of three types: KCl8, KCl8(H2O) and KCl7(H2O)2. The mineral is named as a kalium–thallium ordered compound.

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).

The new alluaudite-group mineral khrenovite with the ideal, end-member formula Na3Fe3+2(AsO4)3 was found in the Arsenatnaya fumarole, Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with aphthitalite-group sulfates, badalovite, calciojohillerite, nickenichite, johillerite, tilasite, svabite, achyrophanite, ozerovaite, pansnerite, arsenatrotitanite, anhydrite, sanidine, hematite, cassiterite, rutile and pseudobrookite. Khrenovite occurs as coarse prismatic crystals up to 0.2 × 0.3 × 0.8 mm and their clusters up to 1 mm across. It is transparent, honey-coloured, red-, orange- or yellow-brown, with vitreous lustre. Khrenovite is brittle, cleavage was not observed. Dcalc is 4.257 g cm–3. Khrenovite is optically biaxial (+), α = 1.825(7), β = 1.834(7), γ = 1.845(7) and 2Vmeas. = 80(10)°. The chemical composition (wt.%, electron-microprobe) is: Na2O 11.47, K2O 1.23, CaO 0.18, MgO 0.01, MnO 4.10, CuO 4.27, ZnO 1.99, Al2O3 0.17, Fe2O3 21.12, SiO2 0.08, P2O5 0.01, V2O5 0.10, As2O5 56.03, SO3 0.02, total 100.78. The empirical formula calculated on the basis of 12 O apfu is (Na2.26K0.16Ca0.02Mn0.35Cu0.33Zn0.15Al0.02Fe3+1.62)Σ4.91(As2.98Si0.01V0.01)Σ3.00O12. Khrenovite is monoclinic, C2/c, a = 12.2394(7), b = 12.7967(5), c = 6.6589(4) Å, β = 112.953(7)°, V = 960.37(10) Å3 and Z = 4. The crystal structure was solved from single-crystal X-ray diffraction data with R1 = 0.0287. Khrenovite is isostructural with other alluaudite-group minerals. Its structural formula simplified to the species-defining constituents is A(1)NaA(2)’NaM(1)NaM(2)Fe3+2(TAsO4)3. The mineral is named in honour of the Russian volcanologist and geologist Anatoly Petrovich Khrenov (1946–2016).

Medvedevite, KMn2+V5+2O6Cl⋅2H2O, is a new mineral discovered in the Toludskoe lava field, formed during the 2012–2013 Tolbachik fissure eruption. The mineral occurs as thin acicular transparent bright red crystals up to 0.15 mm. Medvedevite is associated with thénardite, halite, aphthitalite, leonite, kieserite, eugsterite and syngenite. The empirical formula calculated on the basis of 13+ positive charge units for the anhydrous part and 2H2O is (K1.02Na0.03)Σ1.05Mn2+0.95(V5+1.92S6+0.05Si0.04)Σ2.01O6.02Cl0.96⋅2H2O. The crystal structure of medvedevite was determined using single-crystal X-ray diffraction data: monoclinic crystal system, the space group is P21/c, a = 7.1863(2), b = 10.1147(3), c = 12.7252(4) Å, β = 106.243(3)°, V = 888.04(5) Å3, Z = 4 and R1 = 0.029. The concept of ‘structural unit’ and ‘interstitial complex’ could be applied to the crystal structure of medvedevite. The structural units in medvedevite are based on the high bond-valence V5+O5 polyhedra which share edges and link into [V2O6] chains elongated along the a axis. The interstitial complexes consist of Mn2+, K+ cations and H2O groups and occupy the interstices between structural units. The mineral is optically biaxial (+), with α =1.782(2), β = 1.786(2), γ = 1.792(2), 2V(calc) = 41° (λ = 589 nm). The seven strongest lines of the powder XRD pattern are [d, Å (I, %) (hkl)]: 7.79(100)(011); 5.70(11)(110); 4.75(14)(11$\bar{2}$); 3.89(29)(022); 3.25(53)(031); 2.958(79)(21$\bar{3}$); and 2.850(33)(220). The mineral has been named in honour of the Russian geologist and chemist Robert Alexandrovich Medvedev (1939–2005).

Reznitskyite, ideally CaMg(VO4)F, is a new mineral species of the tilasite group from the Arsenatnaya fumarole, Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It occurs as zones (usually up to 0.05 mm thick) in crystals of V- and P-containing tilasite or as homogeneous grains up to 0.1 mm across. It was found in polymineralic sublimate encrustations in association with minerals of the svabite–fluorapatite–pliniusite system and the schäferite–berzeliite, tilasite–isokite, wagnerite–arsenowagnerite and udinaite–arsenudinaite series. The mineral assemblage also includes calciojohillerite, diopside, forsterite, titanite, rhabdoborite-(V), rhabdoborite-(W), rhabdoborite-(Mo), ludwigite, powellite, scheelite, hematite, baryte and magnesioferrite. Reznitskyite is transparent or semi-transparent, colourless, with vitreous lustre. Dcalc. = 3.453 g cm–3. Under the microscope, in reflected light reznitskyite is grey, non-pleochroic, with very weak bireflectance (ΔR589 nm = 0.5%) and distinct anisotropy. Reznitskyite is the first vanadate with a titanite-type structure. It is monoclinic, space group C2/c, a = 6.6912(7), b = 8.9395(7), c = 7.0587(8) Å, β = 113.078(13)°, V = 388.43(8) Å3 and Z = 4. The strongest reflections of the powder X-ray diffraction pattern are [d in Å(I)(hkl)]: 3.082(100)(200), 3.250(66)($\bar{1}$12, 002), 2.631(44)(022), 2.854(34)($\bar{2}$02), 2.683(33)(130), 3.686(26)(021), 2.531(25)(220), 1.749(25)($\bar{3}$32, $\bar{2}$04) and 2.344(24)(131). Electron microprobe analysis gave (wt.%) MgO 20.44, CaO 26.83, P2O5 6.24, V2O5 21.09, As2O5 18.97, SO3 0.47, F 9.42, –O=F –3.97, with a total of 99.49. The empirical formula of reznitskyite, calculated on the basis of O+F = 5 atoms per formula unit, is: Ca0.97Mg1.03(V0.47As0.33P0.18S0.01)Σ0.99O3.99F1.01. Reznitskyite is a vanadate analogue of tilasite CaMg(AsO4)F and isokite CaMg(PO4)F. The mineral is named in honour of the outstanding Russian mineralogist Leonid Zinovievich Reznitsky (born 1938) who has made significant contribution to the mineralogy of vanadium.

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.

The new alluaudite-group mineral paraberzeliite was found in the Arsenatnaya fumarole, Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. In the deepest zone of Arsenatnaya, paraberzeliite (holotype) is associated with anhydrite, diopside, hematite, svabite, berzeliite, schäferite, calciojohillerite, magnesioferrite, ludwigite, fluorapatite, powellite, baryte, and rhabdoborite-group and aphthitalite-group members. In the middle zone of the fumarole, paraberzeliite occurs with hematite, calciojohillerite, badalovite, johillerite, nickenichite, tilasite, svabite, fluorophlogopite, sanidine, cassiterite, anhydrite, metathénardite and belomarinaite. Paraberzeliite forms prismatic crystals up to 0.2 mm × 0.2 mm × 1 mm often occurring in open-work aggregates. It is transparent, brown (from light to dark brown, sometimes with purple or red hue) or green (from pale greenish to yellow–green). The mineral is brittle, cleavage was not observed. The Mohs hardness is 3½. Dcalc is 3.811 g cm–3. Paraberzeliite is optically biaxial (+), α = 1.718(4), β = 1.728(4), γ = 1.742(4) and 2Vmeas. = 85(5)°. The chemical composition (wt.%, electron-microprobe; holotype) is: Na2O 6.43, CaO 16.65, MgO 11.64, MnO 1.65, CuO 0.06, Fe2O3 2.45, V2O5 1.10, As2O5 59.46, total 99.44. The calculated empirical formula based on 12 O atoms per formula unit is (Na1.20Ca1.71Mg1.66Mn0.13Fe3+0.18)Σ4.88(As2.98V0.07)Σ3.05O12. Paraberzeliite is monoclinic, C2/c, a = 12.3143(7), b = 13.0679(5), c = 6.7717(4) Å, β = 113.657(7)°, V = 998.14(10) Å3 and Z = 4. The crystal structure was solved from single-crystal X-ray diffraction data, R = 0.0349. Paraberzeliite is isostructural with other alluaudite-group minerals. Its simplified crystal chemical formula is A(1)CaA(2)'NaM(1)CaM(2)Mg2(TAsO4)3. The idealised formula is NaCa2Mg2(AsO4)3, or, according to the actual nomenclature of alluaudite-group arsenates, NaCaCaMg2(AsO4)3. The name paraberzeliite reflects the dimorphism of this alluaudite-group mineral with the arsenate garnet berzeliite, ideally (Ca2Na)Mg2(AsO4)3.

The new mineral yurgensonite, ideally K2SnTiO2(AsO4)2, the first natural arsenate with species-defining tin, and the continuous isomorphous series between yurgensonite and katiarsite KTiO(AsO4) are described from sublimates of the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. Yurgensonite and a Sn-bearing variety of katiarsite are associated closely with one another and with badalovite, pansnerite, yurmarinite, achyrophanite, arsenatrotitanite, hatertite, khrenovite, svabite, sanidine, hematite, cassiterite, rutile and aphthitalite-group sulfates. Yurgensonite occurs as sword-shaped crystals up to 0.01 mm × 0.05 mm × 1 mm or acicular to hair-like individuals up to 1 mm long, typically forming radial aggregates up to 2 mm across. It is transparent, colourless, white or pale beige, with vitreous lustre. The mineral is brittle, cleavage was not observed. Dcalc is 3.877 g cm-3. Yurgensonite is optically biaxial (–), α = 1.764(6), β = 1.780(6), γ = 1.792(6) and 2Vmeas. is large. Chemical composition (wt.%, electron-microprobe; holotype) is: Na2O 0.51, K2O 16.27, Rb2O 0.12, Al2O3 0.26, Fe2O3 4.33, SiO2 0.29, TiO2 10.17, SnO2 22.01, P2O5 0.14, V2O5 0.19, As2O5 40.20, Sb2O5 4.88, SO3 0.28, total 99.65. The empirical formula based on 10 O apfu is (K1.92Na0.09Rb0.01)Σ2.02(Sn0.81Ti0.71Fe3+0.30Sb5+0.17Al0.03)Σ2.02(As1.945Si0.03S0.02P0.01V0.01)Σ2.015O10. Yurgensonite is orthorhombic, Pna21, a = 13.2681(6), b = 6.6209(3), c = 10.8113(5) Å, V = 949.74(7) Å3 and Z = 4. The crystal structure was solved from single-crystal X-ray diffraction data, R = 5.02%. Yurgensonite belongs to the KTP-structure type. It is a Ti,Sn-ordered analogue of katiarsite. The structure contains chains of corner-linked alternating crystallographically non-equivalent octahedra M(1) and M(2). In yurgensonite, Sn4+ prevails in the M(2)O6 octahedron whereas the M(1) site is Ti4+-dominant. The new mineral is named in honour of the Russian mineralogist, geochemist and specialist in studies of ore deposits Professor Georgiy Aleksandrovich Yurgenson (born 1935).

The new alluaudite-group mineral calciojohillerite is one of the major arsenates 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. In middle zones of the fumarole, calciojohillerite is associated with hematite, tenorite, johillerite, nickenichite, bradaczekite, badalovite, tilasite, lammerite, ericlaxmanite, aphthitalite-group sulfates, langbeinite, calciolangbeinite, anhydrite, sanidine, fluorophlogopite, fluoborite, cassiterite, pseudobrookite, rutile, sylvite and halite. In deep zones it occurs in association with anhydrite, diopside, hematite, svabite, berzeliite, schäferite, forsterite, magnesioferrite, ludwigite, rhabdoborite-group fluoroborates, powellite, baryte, fluorapatite, udinaite, arsenudinaite and paraberzeliite. Calciojohillerite forms prismatic crystals up to 1 cm long, their aggregates and crystal crusts up to 0.5 m2. It is transparent, colourless, pale green, pale yellow, light blue, pale lilac or pink, with vitreous lustre. The mineral is brittle, with imperfect cleavage. The Mohs hardness is 3½. Dcalc is 3.915 g cm–3. Calciojohillerite is optically biaxial (–), α = 1.719(3), β = γ = 1.732(3); 2Vmeas. = 15(10)°. Chemical composition (wt.%, electron-microprobe; holotype) is: Na2O 7.32, K2O 0.10, CaO 6.82, MgO 20.31, MnO 0.68, CuO 0.27, ZnO 0.02, Al2O3 0.56, Fe2O3 3.53, TiO2 0.01, SiO2 0.03, P2O5 1.25, V2O5 0.10, As2O5 58.77, SO3 0.13, total 99.90. The empirical formula based on 12 O atoms is (Na1.30K0.01Ca0.67Mg2.78Mn0.05Cu0.02Al0.06Fe3+0.24)Σ5.13(As2.83P0.10S0.01V0.01)Σ2.95O12. Calciojohillerite is monoclinic, C2/c, a = 11.8405(3), b = 12.7836(2), c = 6.69165(16) Å, β = 112.425(3)°, V = 936.29(4) Å3 and Z = 4. The crystal structure was solved from single-crystal X-ray diffraction data, R1 = 0.0227. Calciojohillerite is isostructural with other alluaudite-group minerals. Its simplified crystal chemical formula is A(1)CaA(1)′□A(2)□A(2)′NaM(1)MgM(2)Mg2(AsO4)3 (□ = vacancy). The idealised formula is NaCaMg3(AsO4)3, or, according to the nomenclature of alluaudite-group arsenates, NaCaMgMg2(AsO4)3. Calciojohillerite is named as an analogue of johillerite NaCu2+MgMg2(AsO4)3 with species-defining Ca instead of Cu in the ideal formula.

The new alluaudite-group mineral badalovite 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 hematite, tenorite, cassiterite, johillerite, nickenichite, calciojohillerite, bradaczekite, metathénardite, aphthitalite, langbeinite, calciolangbeinite, sanidine, fluorophlogopite, fluoborite, tilasite, anhydrite, pseudobrookite, sylvite, halite, lammerite, urusovite, ericlaxmanite, arsmirandite, svabite, krasheninnikovite, euchlorine, wulffite and alumoklyuchevskite. Badalovite forms oblique-angled prismatic crystals up to 1 mm × 1 mm × 5 mm, typically combined in groups or crusts up to several hundred cm2 in area. The mineral is transparent, green, grey, yellow or colourless, with vitreous lustre. It is brittle, the Mohs hardness is 3½. Cleavage was not observed, the fracture is uneven. Dcalc is 4.02 g cm–3. Badalovite is optically biaxial (–), α = 1.753(3), β = 1.757(3), γ = 1.758(3) and 2Vmeas. = 50(10)°. Chemical composition (wt.%, electron-microprobe; holotype) is: Na2O 9.23, K2O 0.19, CaO 2.04, MgO 13.78, MnO 0.31, CuO 0.12, ZnO 0.24, Al2O3 0.06, Fe2O3 12.77, TiO2 0.01, SiO2 0.06, P2O5 0.33, V2O5 0.05, As2O5 61.51, SO3 0.02, total 100.72. The empirical formula based on 12 O apfu is Na1.67Ca0.20K0.02Mg1.92Zn0.02Mn0.02Cu0.01Fe3+0.90Al0.01(As3.01P0.03Si0.01)Σ3.05O12. The simplified formula is Na2Mg2Fe3+(AsO4)3. Badalovite is monoclinic, C2/c, a = 11.9034(3), b = 12.7832(2), c = 6.66340(16) Å, β = 112.523(3)°, V = 936.59(4) Å3 and Z = 4. The strongest reflections of the powder XRD pattern [d,Å(I)(hkl)] are: 6.41(38)(020), 5.505(20)(200), 3.577(23)($\bar{1}$31), 3.523(25)(310), 3.211(46)($\bar{1}$12), 2.911(28)($\bar{2}$22, $\bar{3}$12), 2.765(100)(240, 400) and 2.618(26)($\bar{1}$32). The crystal structure was solved from single-crystal XRD data with an R1 of = 2.49%. Badalovite is isostructural with other alluaudite-group minerals. Its simplified crystal chemical formula is A(1)NaA(1)’□A(2) □A(2)’NaM(1)MgM(2)(Mg0.5Fe3+0.5)2(AsO4)3 (□ – vacancy) and the end-member formula is NaNaMg(MgFe3+)(AsO4)3. The mineral is named in honour of the outstanding mineralogist and geochemist Stepan Tigranovich Badalov (1919–2014).

A new mineral glikinite, ideally Zn3O(SO4)2, was found in high-temperature exhalative mineral assemblages in the Arsenatnaya fumarole, Second scoria cone of the Great Tolbachik Fissure Eruption (1975–1976), Tolbachik volcano, Kamchatka Peninsula, Russia. Glikinite is associated closely with langbeinite, lammerite-β, bradaczekite, euchlorine, anhydrite, chalcocyanite and tenorite. It is monoclinic, P21/m, a = 7.298(18), b = 6.588(11), c = 7.840(12) Å, β = 117.15(3)°, V = 335.4(11) Å3 and R1 = 0.046. The eight strongest lines of the powder X-ray diffraction pattern [d in Å (I) (hkl)] are: 6.969(56)(00$\bar{1}$), 3.942(52)(101), 3.483(100)(00$\bar{2}$), 3.294(49)(020), 2.936(43)(120), 2.534(63)(201), 2.501(63)(20$\bar{3}$) and 2.395(86)(02$\bar{2}$). The chemical composition determined by electron-microprobe analysis is (wt.%): ZnO 42.47, CuO 19.50, SO3 39.96, total 101.93. The empirical formula calculated on the basis of O = 9 apfu is Zn2.07Cu0.97S1.98O9 and the simplified formula is Zn3O(SO4)2. Glikinite is a Zn,Cu analogue of synthetic Zn3O(SO4)2. The crystal structure of glikinite is based on OZn4 tetrahedra sharing common corners, thus forming [Zn3O]4+ chains. Sulfate groups interconnect [Zn3O]4+ chains into a 3D framework.

Exhalative mineral assemblages from fumaroles of Tolbachik volcano are very rich in anhydrous sulfate minerals of alkali and transition metals. Koryakite, ideally NaKMg2Al2(SO4)6, was found in the Yadovitaya fumarole of the Second scoria cone of the North Breach of the Great Tolbachik Fissure Eruption (1975–1976), Tolbachik volcano, Kamchatka Peninsula, Russia. Koryakite occurs as a product of fumarolic activity and closely associates with euchlorine and langbeinite. Koryakite is trigonal, R$\bar{3}$, a = 8.1124(11), c = 22.704(7) Å and V = 1294.0(5) Å3. The chemical composition determined by electron-microprobe analysis is (wt.%): Na2O 4.27, K2O 5.85, ZnO 0.31, СaO 0.31, CuO 0.76, MgO 10.15, Al2O3 11.47, Fe2O3 2.73, SO3 64.33 and SiO2 0.13, total 100.31. The empirical formula calculated on the basis of 24 O apfu is Na1.03K0.93(Mg1.89Cu0.07Ca0.04Zn0.03)Σ2.03(Al1.68Fe3+0.26)Σ1.94(S6.02Si0.02)Σ6.04O24. No natural or synthetic chemical analogues of koryakite are known to date. The topology of the [M2+2M3+2(SO4)6]2– heteropolyhedral framework in koryakite is very similar to the one in millosevichite, Al2(SO4)3 and mikasaite, Fe3+2(SO4)3. Replacement of part of the trivalent cations in the [M3+2(SO4)3]0 framework by divalent cations gives the framework a negative charge for koryakite and allows the incorporation of the alkali species in the channels. This structural mechanism is reminiscent of the concept of stuffed derivative structures. Koryakite is also structurally related to synthetic NaMgFe3+(SO4)3 and to the broader family of NASICON-related phases.

A new mineral majzlanite, ideally K2Na(ZnNa)Ca(SO4)4, was found in high-temperature exhalative mineral assemblages in the Yadovitaya fumarole, Second scoria cone of the Great Tolbachik Fissure Eruption (1975–1976), Tolbachik volcano, Kamchatka Peninsula, Russia. Majzlanite is associated closely with langbeinite and K-bearing thénardite. Majzlanite is grey with a bluish tint, has a white streak and vitreous lustre. The mineral is soluble in warm water. Majzlanite is monoclinic, C2/c, a = 16.007(2), b = 9.5239(11), c = 9.1182(10) Å, β = 94.828(7)°, V = 1385.2(3) Å3 and Z = 16. The eight strongest lines of the X-ray powder diffraction pattern are [d, Å (I, %)(hkl)]: 3.3721(40)($\bar{3}$12), 3.1473(56)($\bar{4}$02), 3.1062(65)($\bar{2}$22), 2.9495(50)($\bar{1}$31), 2.8736(100)($\bar{1}$13), 2.8350(70)(421), 2.8031(45)(511) and 2.6162(41)($\bar{5}$12). The following structural formula was obtained: K2Na(Zn0.88Na0.60Cu0.36Mg0.16)(Ca0.76Na0.24)(S0.98Al0.015Si0.005O4)4. The chemical composition determined by electron-microprobe analysis is (wt.%): Na2O 9.73, K2O 15.27, ZnO 11.20, CaO 7.03, CuO 4.26, MgO 1.07, Al2O3 0.47, SO3 51.34, SiO2 0.12, total 100.49. The empirical formula calculated on the basis of 16 O apfu is K1.99Na1.93Zn0.84Ca0.77Cu0.33Mg0.16(S3.94Al0.06Si0.01)O16 and the simplified formula is K2Na(Zn,Na,Cu,Mg)Σ2(Ca,Na)(SO4)4. No natural or synthetic compounds directly chemically and/or structurally related to majzlanite are known to date. The topology of the heteropolyhedral framework in majzlanite is complex. An interesting feature of the structure of majzlanite is an edge-sharing of ZnO6 octahedra with SO4 tetrahedra.

The new mineral pansnerite, ideally K3Na3Fe3+6(AsO4)8, 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 aphthitalite, hematite, sanidine, badalovite, khrenovite, achyrophanite, arsenatrotitanite, ozerovaite, tilasite, calciojohillerite, johillerite, nickenichite, svabite, katiarsite, yurmarinite, anhydrite, rutile, cassiterite and pseudobrookite. Pansnerite forms tabular to lamellar (flattened on {010}), usually pseudo-hexagonal crystals up to 0.2 mm × 0.7 mm × 1 mm and crystal clusters up to 2 mm across. It is transparent to translucent, light green, pale greenish, yellowish–greenish or yellowish, with vitreous lustre. The mineral is brittle, with perfect {010} cleavage. The Mohs’ hardness is ca 3. Dcalc is 3.596 g cm–3. Pansnerite is optically biaxial (–), α = 1.702(4), β = 1.713(4), γ = 1.717(4), 2Vmeas = 45(10)° and 2Vcalc = 62°. Chemical composition (holotype, wt.%, electron microprobe data) is: Na2O 6.39, K2O 8.52, CaO 0.08, MgO 0.08, MnO 0.02, NiO 0.02, CuO 1.35, ZnO 0.34, Al2O3 7.35, Cr2O3 0.04, Fe2O3 16.72, SiO2 0.16, P2O5 0.22, V2O5 0.09, As2O5 57.76, SO3 0.04, total 99.20. The empirical formula based on 32 O apfu is K2.86Na3.26Ca0.02(Fe3+3.31Al2.28Cu0.27Zn0.07Mg0.03Cr0.01)Σ5.97(As7.95P0.05Si0.04V0.02S0.01)Σ8.06O32. Pansnerite is orthorhombic, Cmce, a = 10.7372(3), b = 20.8367(8), c = 6.47335(15) Å, V = 1448.27(7) Å3 and Z = 2. The strongest reflections of the X-ray powder diffraction pattern [d,Å(I)(hkl)] are: 10.49(100)(020), 5.380(88)(111), 4.793(65)(220), 3.105(46)(311, 002), 3.079(32)(112, 061), 2.932(35)(260), 2.783(65)(202) and 2.694(52)(400, 222). The crystal structure was solved from single-crystal X-ray diffraction data, R1 = 2.82%. The structure is based on heteropolyhedral layers formed by MO6 octahedra (M = Fe3+ and Al) sharing common vertices and connected by AsO4 tetrahedra. Na+ and K+ cations are located in the interlayer space. The mineral is named in honour of the German–Russian mineralogist and geographer Lavrentiy Ivanovich Pansner (1777–1851). Pansnerite forms a solid-solution series with the isotypic mineral ozerovaite, ideally KNa2Al3(AsO4)4.

Aleutite, ideally [Cu5O2](AsO4)(VO4)·(Cu0.5□0.5)Cl, was found in the Yadovitaya fumarole of the Second scoria cone of the Great Fissure Tolbachik eruption, Kamchatka Peninsula, Russia. Aleutite occurs as individual crystals in the masses of polycrystalline anhydrite. Aleutite is monoclinic, C2/m, a = 18.090(2) Å, b = 6.2284(6) Å, c = 8.2465(9) Å, β = 90.597(2)°, V = 929.1(2) Å3 and Z = 4 (from single-crystal X-ray diffraction data). The empirical formula calculated on the basis of (As + V+Mo + Fe3+) = 2 atoms per formula unit is Сu5.40Zn0.05Ca0.01As1.09V0.84Mo0.04Fe0.03K0.05Pb0.02Rb0.01Cs0.01O9.97Cl1.07. The crystal structure was solved by direct methods and refined to an agreement index R1 = 0.066. Aleutite has a new structure type. Aleutite is unique amongst natural and synthetic copper vanadates and arsenates, as it has As5+ and V5+ cations ordered over two tetrahedral sites. The topology of ${}_\infty ^1 [{\rm Cu_5O_2}]^{6 +} $ oxocentred bands in aleutite is novel and has not been described before in minerals and synthetic materials. The structural architecture of the ${}_\infty ^1 [{\rm Cu_5O_2}]^{6 +} $ band in aleutite can be derived from a kagome network and represents a one-dimensional slice from it. In addition, aleutite is an interesting and complex example of a natural salt-inclusion phase.

Dokuchaevite, ideally Cu8O2(VO4)3Cl3, was found in the Yadovitaya fumarole of the Second scoria cone of the North Breach of the Great Tolbachik Fissure Eruption (1975–1976), Tolbachik volcano, Kamchatka Peninsula, Russia. Dokuchaevite occurs on the crusts of various copper sulfate exhalative minerals (such as kamchatkite and euchlorine) as individual prismatic crystals. Dokuchaevite is triclinic, P$\bar{1}$, a = 6.332(3), b = 8.204(4), c = 15.562(8) Å, α = 90.498(8), β = 97.173(7), γ = 90.896(13)°, V = 801.9(7) Å3 and R1 = 0.057. The eight strongest lines of the X-ray powder diffraction pattern are (d, Å (I)(hkl): (15.4396)(18)(00$\bar{1}$), (7.2762)(27)(0$\bar{1}$1), (5.5957)(43)(012), (4.8571)(33)($\bar{1}\bar{1}$1), (3.1929) (29)(023), (2.7915)(30)(202), (2.5645)(21)(032), (2.5220)(100)(1$\bar{3}$0), (2.4906)(18)(130) and (2.3267)(71)(2$\bar{2}$2). The chemical composition determined by electron-microprobe analysis is (wt.%): CuO 60.87, ZnO 0.50, FeO 0.36, V2O5 19.85, As2O5 6.96, SO3 0.44, MoO3 1.41, SiO2 0.20, P2O5 0.22, Cl 10.66, –O = Cl2 2.41, total 99.06. The empirical formula calculated on the basis of 17 anions per formula unit is (Cu7.72Zn0.06Fe0.05)Σ7.83(V2.20As0.61Mo0.10S0.06P0.03Si0.03)Σ3.03O13.96Cl3.04.

The crystal structure of dokuchaevite represents a new structure type with eight Cu sites, which demonstrate the remarkable diversity of Cu2+ mixed-ligand coordination environments. The crystal structure of dokuchaevite is based on OCu4 tetrahedra that share common corners thus forming [O2Cu6]8+ single chains. Two of the eight symmetrically independent copper atoms do not form Cu–O bonds with additional oxygen atoms, and thus are not part of the OCu4 tetrahedra, but provide the three-dimensional integrity of the [O2Cu6]8+ chains into a framework. TO4 mixed tetrahedral groups are located within the cavities of the framework. The structural formula of dokuchaevite can be represented as Cu2[Cu6O2](VO4)3Cl3.

The new mineral zubkovaite, Ca3Cu3(AsO4)4, 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 anhydrite, svabite, hematite, johillerite, tilasite, fluorophlogopite, sanidine and aphthitalite. Zubkovaite occurs as coarse prismatic crystals up to 0.01 mm × 0.01 mm × 0.2 mm combined in radiating aggregates or crusts. The mineral is transparent, bright sky-blue, turquoise-coloured or light bluish-green, with vitreous lustre. It is brittle, with imperfect cleavage. The Mohs’ hardness is ca 3. Dcalc is 4.161 g cm–3. Zubkovaite is optically biaxial (–), α = 1.747(5), β = 1.774(5), γ = 1.792(5) and 2Vmeas = 75(10)°. Chemical composition (wt.%, electron microprobe) is: CaO 19.22, CuO 27.37, As2O5 52.54, SO3 0.67, total 99.80. The empirical formula based on 16 O apfu is Ca2.96Cu2.97(As3.945S0.07)Σ4.015O16. Zubkovaite is monoclinic, C2, a = 16.836(3), b = 5.0405(8), c = 9.1173(17) Å, β = 117.388(13)°, V = 687.0(2) Å3 and Z = 2. The strongest reflections of the powder XRD pattern [d,Å (I) (hkl)] are: 7.44 (100) ($\bar 2$01), 3.727 (79) (400, $\bar 2$02, $\bar 3$11), 3.334 (92) ($\bar 1$12), 2.914 (73) (311), 2.765 (50) ($\bar 6$01, $\bar 6$02), 2.591 (96) ($\bar 3$13) and 2.521 (53) (020). The crystal structure is unique for minerals. It was solved from single-crystal X-ray diffraction data to R = 7.19%. The structure contains trimers of Cu2+-centred polyhedra (consisting of one distorted square CuO4 in the core and two distorted square pyramids CuO5) and two crystallographically independent As5+O4 tetrahedra playing different roles: As(2)O4 tetrahedra link neighbouring trimers into ribbons whereas As(1)O4 tetrahedra link adjacent ribbons into heteropolyhedral layers; Ca cations are located in the interlayer space. The mineral is named in honour of the Russian crystallographer and crystal chemist Natalia Vital'evna Zubkova (born 1976).