This paper is the first description of natural copper-rich oxide spinels. They were found in deposits of oxidizing-type fumaroles related to the Tolbachik volcano, Kamchatka, Russia. This mineralization is represented by nine species with the following maximum contents of CuO (wt.%, given in parentheses): a new mineral thermaerogenite, ideally CuAl₂O₄ (26.9), cuprospinel, ideally CuFe³⁺₂O₄ (28.6), gahnite (21.4), magnesioferrite (14.7), spinel (10.9), magnesiochromite (9.0), franklinite (7.9), chromite (5.9), and zincochromite (4.8). Cuprospinel, formerly known only as a phase of anthropogenic origin, turned out to be the Cu-richest natural spinel-type oxide [sample with the composition (Cu_0.831Zn_0.100Mg_0.043Ni_0.022)_Σ0.996(Fe³⁺_1.725Al_0.219Mn³⁺_0.048Ti_0.008)_Σ2.000O₄ from Tolbachik]. Aluminum and Fe³⁺-dominant spinels (thermaerogenite, gahnite, spinel, cuprospinel, franklinite, and magnesioferrite) were deposited directly from hot gas as volcanic sublimates. The most probable temperature interval of their crystallization is 600–800 °C. They are associated with each other and with tenorite, hematite, orthoclase, fluorophlogopite, langbeinite, calciolangbeinite, aphthitalite, anhydrite, fluoborite, sylvite, halite, pseudobrookite, urusovite, johillerite, ericlaxmanite, tilasite, etc. Cu-bearing spinels are among the latest minerals of this assemblage: they occur in cavities and overgrow even alkaline sulfates. Cu-enriched varieties of chrome-spinels (magnesiochromite, chromite, and zincochromite) were likely formed in the course of the metasomatic replacement of a magmatic chrome-spinel in micro-xenoliths of ultrabasic rock under the influence of volcanic gases. The new mineral thermaerogenite, ideally CuAl₂O₄, was found in the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption. It forms octahedral crystals up to 0.02 mm typically combined in open-work clusters up to 1 mm across. Thermaerogenite is semitransparent to transparent, with a strong vitreous lustre. Its colour is brown, yellow-brown, red-brown, brown-yellow or brown-red. The mineral is brittle, with the conchoidal fracture, cleavage is none observed. D(calc.) is 4.87 g/cm³. The chemical composition of the holotype (wt.%, electron microprobe) is: CuO 25.01, ZnO 17.45, Al₂O₃ 39.43, Cr₂O₃ 0.27, Fe₂O₃ 17.96, total 100.12 wt.%. The empirical formula calculated on the basis of 4 O apfu is: (Cu_0.619Zn_0.422)_Σ1.041(Al_1.523Fe³⁺_0.443Cr_0.007)_Σ1.973O₄. The mineral is cubic, Fd-3m, a = 8.093(9) Å, V = 530.1(10) ų. Thermaerogenite forms a continuous isomorphous series with gahnite. The strongest lines of the powder X-ray diffraction pattern of thermaerogenite [d, Å (I, %) (hkl)] are: 2.873 (65) (220), 2.451 (100) (311), 2.033 (10) (400), 1.660 (16) (422), 1.565 (28) (511) and 1.438 (30) (440).

Ferrisanidine, K[Fe³⁺Si₃O₈], the first natural feldspar with species-defining iron, is an analogue of sanidine bearing Fe³⁺ instead of Al. It was found in exhalations of the active Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Fissure Tolbachik Eruption, Tolbachik volcano, Kamchatka Peninsula, Russia. The associated minerals are aegirine, cassiterite, hematite, sylvite, halite, johillerite, arsmirandite, axelite, aphthitalite. Ferrisanidine forms porous crusts composed by cavernous short prismatic crystals or irregular grains up to 10 μm × 20 μm. Ferrisanidine is transparent, colorless to white, the lustre is vitreous. D_calc is 2.722 g·cm⁻³. The chemical composition of ferrisanidine (wt. %, electron microprobe) is: Na₂O 0.25, K₂O 15.15, Al₂O₃ 0.27, Fe₂O₃ 24.92, SiO₂ 60.50, in total 101.09. The empirical formula calculated based on 8 O apfu is (K_0.97Na_0.03)_Ʃ1.00(Si_3.03Fe³⁺_0.94Al_0.02)_Ʃ3.99O₈. The crystal structure of ferrisanidine was studied using the Rietveld method, the final R indices are: R_p = 0.0053, R_wp = 0.0075, R₁ = 0.0536. Parameters of the monoclinic unit cell are: a = 8.678(4), b = 13.144(8), c = 7.337(5) Å, β = 116.39(8)°, V = 749.6(9) ų. Space group is C2/m. The crystal structure of ferrisanidine is based on the sanidine-type “ferrisilicate” framework formed by disordered [SiO₄] and [Fe³⁺O₄] tetrahedra.

The crystal structure of the Ag-exchanged form of the zirconosilicate with the simplified formula (Na_6-2xCa_x▯_x)Zr₃[Si₉O₂₇] with x < 1 (the idealized formula Na₆Zr₃[Si₉O₂₇]), a product of thermal transformation of catapleiite, ideally Na₂Zr[Si₃O₉]·2H₂O, was studied using single crystal X-ray diffraction data. The crystal structure of Na₆Zr₃[Si₉O₂₇] is based on a heteropolyhedral framework built by nine-membered tetrahedral rings [Si₉O₂₇] and isolated [ZrO₆] octahedra. This zirconosilicate demonstrates high exchange capacity to Ag (experiment with 1 M AgNO₃ aqueous solution, 250 °C, 30 days). Its Ag-exchanged form with the simplified formula (Ag₅Ca_0.5)Zr₃[Si₉O₂₇] is characterized by a significant distortion of the heteropolyhedral framework and strongly disordered arrangement of extra-framework cations (Ag) which results in the doubling of a parameter of the hexagonal unit cell [a = 23.3462(3), c = 10.10640(10) Å, V = 4770.45(13) ų] and space group P6₃cm. Ag⁺ cations preferably occupy the sites that are close to the Na sites in Na₆Zr₃[Si₉O₂₇].

Two new isostructural minerals udinaite and arsenudinaite with the end-member formulae NaMg₄(VO₄)₃ and NaMg₄(AsO₄)₃, respectively, are found in the Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. They are associated with one another and anhydrite, diopside, hematite, schäferite, berzeliite, svabite, calciojohillerite, tilasite, reznitskyite, ludwigite, rhabdoborite-group borates, forsterite, magnesioferrite, fluorapatite, pliniusite, and powellite. Both minerals occur as equant tetragonal prismatic–dipyramidal crystals up to 0.15 mm, aggregates up to 1 cm and interrupted crusts up to 2 × 2 cm². Udinaite and arsenudinaite, visually indistinguishable from one another, are transparent, beige or brownish-yellowish, with vitreous lustre. Both minerals are optically uniaxial (–); ω = 1.785/1.777 and ε = 1.830/1.820, D_calc. = 3.613/3.816 g·cm⁻³ (udinaite/arsenudinaite). The empirical formulae are: udinaite: (Na_0.55Ca_0.16)_Σ0.71(Mg_4.04Mn_0.02Fe_0.01)_Σ4.07(V_1.63As_1.05P_0.28Si_0.03S_0.01)_Σ3.00O₁₂; arsenudinaite: (Na_0.57Ca_0.13)_Σ0.70(Mg_4.01Mn_0.01Fe_0.01)_Σ4.03(As_2.07V_0.84P_0.10Si_0.01S_0.01)_Σ3.03O₁₂. Both minerals are tetragonal, I-42d, Z = 4, a = 6.8011(2)/6.8022(1), c = 19.1839(12)/19.1843(6) Å, and V = 887.35(7)/887.66(4) ų, R₁ = 0.0287/0.0119 (udinaite/arsenudinaite). Their crystal structure consists of the helical chains of edge-sharing MgO₆ octahedra and isolated TO₄ tetrahedra, forming a heteropolyhedral pseudo-framework with Na cations located in cavities. Both minerals are isostructural to jeffbenite. Udinaite and arsenudinaite form an isomorphous series in which the contents of T constituents vary within (in apfu): V_1.6–0.1As_2.8–1.0P_0.4–0.0.

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 (Na_3.64K_0.09Pb_0.03)_Σ3.76(Cu_0.51Ca_0.22Mg_0.16Zn_0.07Al_0.01Mn_0.01)_Σ0.98S_3.04O₁₂. 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) ų, space group R3 and Z = 18. The crystal structure was studied using the Rietveld method, R_p = 0.0246, R_wp = 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.