Evgeny G. Sidorov

New arsenate minerals from the Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. I. Yurmarinite, Na7(Fe3+,Mg,Cu)4(AsO4)6

Abstract A new mineral, yurmarinite, Na7(Fe3+,Mg,Cu)4(AsO4)6, occurs 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 hatertite, bradaczekite, johillerite, hematite, tenorite, tilasite and aphthitalite. Yurmarinite occurs as well-shaped, equant crystals up to 0.3 mm in size, their clusters up to 0.5 mm and thin, interrupted crystal crusts up to 3 mm × 3 mm on volcanic scoria. Crystal forms are {101}, {011}, {100}, {110} and {001}. Yurmarinite is transparent, pale green or pale yellowish green to colourless. The lustre is vitreous and the mineral is brittle. The Mohs hardness is ~4½. One direction of imperfect cleavage was observed, the fracture is uneven. D(calc.) is 4.00 g cm-3. Yurmarinite is optically uniaxial (-), ω = 1.748(5), ε = 1.720(3). The Raman spectrum is given. The chemical composition (wt.%, electron microprobe data) is Na2O 16.85, K2O 0.97, CaO 1.28, MgO 2.33, MnO 0.05, CuO 3.17, ZnO 0.97, Al2 O3 0.99, Fe2O3 16.44, TiO2 0.06, P2O5 0.12, V2O5 0.08, As2O5 56.68, total 99.89. The empirical formula, calculated on the basis of 24 O atoms per formula unit, is (Na6.55Ca0.28K0.22)∑7.05(Fe3+2.48Mg0.70Cu0.48Al0.23Zn0.14 Ti0.01Mn0.01)∑4.05(As5.94P0.02V0.01)∑5.97O24. Yurmarinite is rhombohedral, R3̅ c, a = 13.7444(2), c = 18.3077(3) Å, V = 2995.13(8) Å3, Z = 6. The strongest reflections in the X-ray powder pattern [d,Å (I)(hkl)] are: 7.28(45)(012); 4.375(33)(211); 3.440(35)(220); 3.217(36)(131,214); 2.999(30)(223); 2.841(100)(125); 2.598(43)(410). The crystal structure was solved from single-crystal X-ray diffraction data to R = 0.0230. The structure is based on a 3D heteropolyhedral framework formed by M4O18 clusters (M = Fe3+ > Mg,Cu) linked with AsO4 tetrahedra. Sodium atoms occupy two octahedrally coordinated sites in the voids of the framework. In terms of structure, yurmarinite is unique among minerals but isotypic with several synthetic compounds with the general formula (Na7-x⃞x)(M3+3+xM2+1-x)(T5+O4)2 in which T = As or P, M3+ = Fe or Al, M2+ = Fe and 0 ≤ x ≤ 1. The mineral is named in honour of the Russian mineralogist, petrologist and specialist in studies of ore deposits, Professor Yuriy B. Marin (b. 1939). The paper also contains a description of the Arsenathaya fumarole and an overview of arsenate minerals formed in volcanic exhalations.

New arsenate minerals from the Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. IV. Shchurovskyite, K2CaCu6O2(AsO4)4 and dmisokolovite, K3Cu5AlO2(AsO4)4

Abstract Two new minerals shchurovskyite, ideally K2CaCu6O2(AsO4)4, and dmisokolovite, ideally K3Cu5AlO2(AsO4)4, are 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 Peninsula, Russia. They are associated with one another and with johillerite, bradaczekite, tilasite, melanarsite, tenorite, hematite, aphthitalite, langbeinite, orthoclase, etc. Shchurovskyite occurs as coarse tabular or prismatic crystals up to 0.15 mm in size or anhedral grains forming parallel aggregates and crusts up to 1.5 cm × 2 cm across. Dmisokolovite forms tabular, prismatic or dipyramidal crystals up to 0.2 mm in size, commonly combined in clusters or crusts up to 0.7 cm × 1.5 cm across. Both minerals are transparent with a vitreous lustre. They are brittle, with Mohs’ hardness ≈ 3. Shchurovskyite is olive-green or olive drab. Dmisokolovite is bright emerald-green to light green. Dcalc = 4.28 (shchurovskyite) and 4.26 (dmisokolovite) g cm−3. Both are optically biaxial; shchurovskyite: (+), α = 1.795(5), β = 1.800(5), γ = 1.810(6), 2Vmeas = 70(15)°; dmisokolovite: (−), α = 1.758(7), β = 1.782(7), γ = 1.805(8), 2Vmeas = 85(5)°. The Raman spectra are given. Chemical data (wt.%, electron-microprobe; first value is for shchurovskyite, second for dmisokolovite):Na2O 0.00, 0.83;K2O 8.85, 10.71; Rb2O 0.11, 0.00;MgO 0.00, 0.35; CaO 4.94, 0.21; CuO 43.19, 38.67; ZnO 0.42, 0.20; Al2O3 0.04, 4.68; Fe2O3 0.00, 0.36; P2O5 0.59, 0.78; V2O5 0.01, 0.04; As2O5 40.72, 43.01; SO3 0.35, 0.00; total 99.22, 99.84. The empirical formulae, based on 18 O a.p.f.u., are shchurovskyite: K2.05Rb0.01Ca0.96Cu5.92Zn0.06Al0.01P0.09S0.05As3.86O18; dmisokolovite: Na0.28K2.36Mg0.09C a0.04Cu5.04Zn0.04 Al0.95Fe0.053+P0.11As3.88O18. The strongest reflections of X-ray powder patterns [d,Å(I)(hkl)] are shchurovskyite: 8.61(100)(200, 001), 5.400(32)(110), 2.974(32)(3̅12, 510), 2.842(47)(003, 020), 2.757(63) (6̅01, 511), 2.373(36)(512, 420) and 2.297(31)( 4̅21, 2̅22, 313); dmisokolovite: 8.34(95)(002), 5.433(84)(110), 2.921(66)(510, 3̅14), 2.853(58)(511, 020) and 2.733(100)(006, 512, 6̅02). Shchurovskyite is monoclinic, C2, a = 17.2856(9), b = 5.6705(4), c = 8.5734(6) Å, β = 92.953(6)°, V = 839.24(9) Å3 and Z = 2. Dmisokolovite is monoclinic, C2/c, a = 17.0848(12), b = 5.7188(4), c = 16.5332(12) Å, β = 91.716(6)°, V = 1614.7(2) Å3 and Z = 4. Their crystal structures [single-crystal X-ray diffraction data, R = 0.0746 (shchurovskyite) and 0.1345 (dmisokolovite: model)] are closely related in the topology of the main building units. They are based on a quasi-framework consisting of AsO4 tetrahedra and polyhedra centred by Cu in shchurovskyite or by Cu and Al in dmisokolovite. K and Ca are located in channels of the quasi-framework. The minerals are named in honour of outstanding Russian geologists and mineralogists Grigory Efimovich Shchurovsky (1803−1884) and Dmitry Ivanovich Sokolov (1788-1852).

New arsenate minerals from the Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. II. Ericlaxmanite and kozyrevskite, two natural modifications of Cu4O(AsO4)2

Abstract Two new minerals, ericlaxmanite and kozyrevskite, dimorphs of Cu4O(AsO4)2, were 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. They are associated with each other and with urusovite, lammerite, lammerite-b, popovite, alarsite, tenorite, hematite, aphthitalite, langbeinite, As-bearing orthoclase, etc. Ericlaxmanite occurs as tabular, lamellar, equant or short prismatic crystals up to 0.1 mm in size, their clusters and pseudomorphs after urusovite crystal crusts up to 1.5 cm × 2 cm in area. Kozyrevskite occurs as prismatic crystals up to 0.3 mm long in clusters and as individual crystals. Both minerals are transparent with a vitreous lustre. They are brittle, with Mohs’ hardness ~3½. Ericlaxmanite is green to dark green. Kozyrevskite is bright grass green to light yellowish green; Dcalc is 5.036 (ericlaxmanite) and 4.934 (kozyrevskite) g cm-3. Both minerals are optically biaxial (–); ericlaxmanite: α = 1.870(10), β = 1.900(10), γ = 1.915(10), 2Vmeas = 60(15)°; kozyrevskite: α = 1.885(8), β = 1.895(8), γ = 1.900(8), 2Vmeas. = 75(10)°. The Raman spectra are given. Chemical data (wt.%, electron microprobe; the first value is for ericlaxmanite, the second for kozyrevskite): CuO 57.55, 58.06; ZnO 0.90, 1.04; Fe2O3 0.26, 0.12; SiO2 n.d., 0.12; P2O5 0.23, 1.23; V2O5 0.14, 0.37; As2O5 40.57, 38.78; SO3 0.17, 0.43; total 99.82, 100.15. The empirical formulae, based on 9 O a.p.f.u., are: ericlaxmanite: (Cu3.97Zn0.06Fe0.02)∑4.05(As1.94P0.02V0.01S0.01)∑1.98O9 and kozyrevskite: (Cu3.95Zn0.07Fe0.01)∑4.03(As1.83P0.09S0.03V0.02Si0.01)∑1.98O9. Ericlaxmanite is triclinic, P1̄ , a = 6.4271(4), b = 7.6585(4), c = 8.2249(3) Å , α = 98.396(4), β = 112.420(5), γ = 98.397(5)°, V = 361.11(3) Å3 and Z = 2. Kozyrevskite is orthorhombic, Pnma, a = 8.2581(4), b = 6.4026(4), c = 13.8047(12) Å , V = 729.90(9) Å3 and Z = 4. The strongest reflections in the X-ray powder patterns [d Å (I)(hkl)] are: ericlaxmanite: 3.868(46)(101), 3.685(100)(020), 3.063(71)(012), 2.957(58)(02̄ 2), 2.777(98)(2̄ 12, 2̄1 1), 2.698(46)(2̄1̄2) and 2.201(51)(013, 031); kozyrevskite: 3.455(100)(004), 3.194(72)(020, 104), 2.910(69)(022), 2.732(82)(122), 2.712(87)(301) and 2.509(92)(123). Their crystal structures, solved from single-crystal X-ray diffraction data [R = 0.0358 (ericlaxmanite) and 0.1049 (kozyrevskite)], are quite different. The ericlaxmanite structure is based on an interrupted framework built by edge- and corner-sharing Cu-centred, distorted tetragonal pyramids, trigonal bipyramids and octahedra. The kozyrevskite structure is based on complicated ribbons of Cu-centred distorted tetragonal pyramids and trigonal bipyramids. Ericlaxmanite is named in honour of the Russian mineralogist, geologist, geographer, biologist and chemist Eric Laxman (1737-1796). Kozyrevskite is named in honour of the Russian geographer, traveller and military man Ivan Petrovich Kozyrevskiy (1680-1734), one of the first researchers of Kamchatka.

New arsenate minerals from the Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. III. Popovite, Cu5O2(AsO4)2

Abstract The new mineral popovite, Cu5O2(AsO4)2, was found in the 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 ericlaxmanite, kozyrevskite, urusovite, lammerite, lammerite-b, johillerite, bradaczekite, tenorite, hematite, aphthitalite, anhydrite, langbeinite, calciolangbeinite, As-bearing orthoclase, etc. Popovite occurs as prismatic or tabular crystals and as grains up to 0.2 mm in size forming clusters up to 1.5 mm in size and as crusts on basalt scoria or on aphthitalite incrustations. Popovite is transparent with a vitreous to greasy lustre. Its colour is olive green to dark olive-green, but fine-grained varieties are light yellow-green. The mineral is brittle, with Mohs’ hardness ~3 ½. Cleavage was not observed and the fracture is uneven. Dcalc is 5.30 g cm-3. Popovite is optically biaxial (+), α = 1.84(1), β ≈ 1.86, γ = 1.96(1), 2Vmeas = 50(20)°. The Raman spectrum is given. Chemical data (wt.%, electron-microprobe) are CuO 63.28, ZnO 0.56, V2O5 0.12, As2O5 35.80, SO3 0.27, total 100.03. The empirical formula, based on 10 O a.p.f.u., is (Cu4.99Zn0.04)S5.03(As1.95S0.02V0.01)S1.98O10. Popovite is triclinic, P1̄, a = 5.1450(3), b = 6.2557(3), c = 6.2766(4) Å, α = 100.064(5), β = 96.351(5), γ = 95.100(5)°, V = 196.47(1) Å3 and Z = 1. The strongest reflections in the powder X-ray diffraction pattern [d,Å (I)(hkl)] are 3.715(36)(110, 101), 3.465(43)(11̄1), 2.968(90)(01̄2), 2.927(100)(111), 2.782(31)(1̄02), 2.768(67)(1̄20), 2.513(55)(1̄2̄1) and 2.462(67)(2̄01). Popovite has a novel structure type. Its crystal structure, solved from single-crystal X-ray diffraction data (R = 0.0459), is based on (010) layers forming an interrupted framework. The layer consists of Cu(1)O6 octahedra with very strong Jahn-Teller distortion and Cu(2)O5 and Cu(3)O5 polyhedra. The linkage between the layers is reinforced by isolated AsO4 tetrahedra. Popovite is named in honour of the Russian mineralogists Vladimir Anatol’evich Popov (b. 1941) and Valentina Ivanovna Popova (b. 1941), a husband and wife research team working in the Institute of Mineralogy of the Urals Branch of the Russian Academy of Sciences, Miass, Russia.

New arsenate minerals from the Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. V. Katiarsite, KTiO(AsO4)

Abstract A new mineral katiarsite, ideally KTiO(AsO4), occurs 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 hatertite, bradaczekite, johillerite, yurmarinite, tilasite, arsmirandite, hematite, tenorite, As-bearing orthoclase, fluorophlogopite and aphthitalite. Katiarsite occurs as long prismatic to acicular, typically sword-like, crystals up to 3 μm×10 μm×50 μmin size, and rarely up to 0.15 mm long. Crystal forms are {011}, {201}, {100} and {001}. Katiarsite is transparent, colourless, with a vitreous lustre. The mineral is brittle. Cleavage was not observed, the fracture is uneven. Dcalc is 3.49 g cm-3. Katiarsite is optically biaxial (+), α = 1.784(3), β = 1.792(3), γ = 1.870(5); 2Vobs is small. Orientation is X=b, Y = a, Z = c. The Raman spectrum is reported. The chemical composition (wt.%, electron-microprobe data) is K2O 18.98, Fe2O3 5.07, TiO2 27.49, As2O5 47.48, total 99.02. The empirical formula, calculated based on 5 O apfu, is K1.00(Ti0.85Fe0.163+ )Σ1.01As1.02O5. The strongest reflections of the powder X-ray diffraction pattern [d,Å(I )(hkl)] are 5.91(17)(110), 5.62(74)(011), 4.18(19)(202), 3.157(66) (013), 2.826(100)(221), 2.809(96)(022) and 2.704(19)(004). Katiarsite is orthorhombic, a = 13.174(4), b = 6.5635(10), c = 10.805(2) Å, V = 934.3(3) Å3, Z = 8, space group Pna21, by analogy with KTA, synthetic KTiO(AsO4), a notable non-linear optical crystalline material. The name of the mineral reflects its chemical composition, kalium titanyl arsenate.

Kaliochalcite, KCu2(SO4)2[(OH)(H2O)], a new tsumcorite-group mineral from the Tolbachik volcano, Kamchatka, Russia

The new tsumcorite-group mineral kaliochalcite, KCu 2 (SO 4 ) 2 [(OH)(H 2 O)] (IMA 2013–037), is found in several fumaroles at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. Two fumaroles, Yadovitaya and Arsenatnaya, are considered as its type localities. The mineral seems to be a product of the interactions involving the high-temperature, sublimate KCu-sulphates and atmospheric water vapour at temperatures not higher than 100–150°C. Kaliochalcite mostly occurs in polymineralic crusts (up to several dozens cm 2 in area and up to 0.5 cm thick), where it is typically the major component. The mineral forms fine-grained pseudomorphs after anhydrous KCu-sulphates, mainly euchlorine, fedotovite or piypite, usually with their relics. Other associated minerals are hematite, tenorite, langbeinite, aphthitalite, steklite, lammerite, chlorothionite, gypsum, etc . Pseudo-rhombohedral or more complicated crystals of kaliochalcite (commonly up to 0.02 × 0.04 mm, rarely up to 0.03 × 0.1 mm) are observed in cavities. The mineral is light green, bright grass-green or almost colourless. Kaliochalcite is transparent in individuals and translucent in aggregates, with vitreous lustre. It is brittle, the Mohs’ hardness is 4. No cleavage was observed, the fracture is uneven. The caculated density, D calc , is 3.49 g cm −3 . Kaliochalcite is optically biaxial (+), α 1.630(3), β 1.650(3), γ 1.714(3), 2 V meas 55(10)°. The IR spectrum is given. The chemical composition (wt%, electron-microprobe data, H 2 O by selective sorption from the gaseous products of heating) is: Na 2 O 0.04, K 2 O 11.01, CaO 0.27, FeO 0.15, CuO 40.28, ZnO 0.39, SO 3 40.97, H 2 O 5.84, total 98.95. The empirical formula, calculated on the basis of 10 O apfu , is: (K 0.94 Ca 0.02 Na 0.01 ) Σ0.97 (Cu 2.03 Zn 0.02 Fe 0.01 ) Σ2.06 S 2.05 O 8.20 (OH) 1.01 (H 2 O) 0.79 . Kaliochalcite is monoclinic, space group C 2/ m, a 8.935(2), b 6.252(2), c 7.602(2) A, β 117.318(5)°, V 377.3(2) A 3 and Z = 2. The strongest reflections of the X-ray powder pattern [ d ,A( I )( hkl )] are: 6.78(100)(001), 3.484(70)(20–2), 3.249(63)(11–2), 2.892(77)(201), 2.852(83)(02–l), 2.554(72)(31–2, 22–1), 2.326(44)(22–2) and 1.693(37)(42–3, 22–4). The crystal structure was solved from single-crystal X-ray diffraction data, R = 0.100. The structure is built up from chains of edge-sharing Cu 2+ O 6 Jahn-Teller distorted octahedra connected by SO 4 tetrahedra and H-bonds to form {Cu 2 (SO 4 ) 2 [(OH)(H 2 O]} − layers. The linkage between these layers is provided by K + cations and H-bonds. Kaliochalcite is named as the potassium analogue of natrochalcite.

Chrysothallite K6Cu6Tl3+Cl17(OH)4·H2O, a new mineral species from the Tolbachik volcano, Kamchatka, Russia

Abstract A new mineral chrysothallite K6Cu6Tl3+Cl17(OH)4 · H2O was found in two active fumaroles, Glavnaya Tenoritovaya and Pyatno, at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. Chrysothallite seems to be a product of the interactions involving high-temperature sublimate minerals, fumarolic gas and atmospheric water vapour at temperatures not higher than 150 °C. It is associated with belloite, avdoninite, chlorothionite, sanguite, eriochalcite, mitscherlichite, sylvite, camallite and kainite at Glavnaya Tenoritovaya and with belloite, avdoninite, chlorothionite, eriochalcite, atacamite, halite, krohnkite, natrochalcite, gypsum and antlerite at Pyatno. The mineral forms equant-to-thick tabular crystals up to 0.05 mm, typically combined in clusters or crusts up to 1 mm across. Crystal forms are: {001}, {100}, {110}, {101} and {102}. Chrysothallite is transparent, bright golden-yellow to light yellow in finely crystalline aggregates. The lustre is vitreous. The mineral is brittle. Cleavage was not observed, the fracture is uneven. Dmeas= 2.95(2), Dcalc = 2.97 g cm-3. Chrysothallite is optically uniaxial (+), ω = 1.720(5), ε = 1.732(5). The Raman spectrum is given. The chemical composition (wt.%, electron-microprobe data, H2O calculated based on the crystal structure data) is: K 15.92, Cu 24.56, Zn 1.38, Tl 13.28, Cl 40.32, H2O(calc.) 3.49, total 98.95. The empirical formula, calculated on the basis of 17 Cl + 5 O a.p.f.u., is: K6.09(Cu5.78Zn0.32)∑6.10Tl0.97Cl17[(OH)3.80O0.20]· H2O. Chrysothallite is tetragonal, I4/mmm, a = 11.3689(7), c = 26.207(2) Å, V = 3387.3(4) Å3, Z = 4. The strongest reflections of the powder X-ray pattern [d,Å(I)(hkl)] are: 13.20(44)(002); 6.88(100)(112); 5.16(30)(202, 114); 4.027(25)(220); 3.471(28)(206), 3.153(30)(314), 3.075(47)(305), 2.771 (38)(316). The crystal structure (solved from single-crystal X-ray diffraction data, R = 0.0898) is unique. Its basic structural unit is a (001) layer of edge-sharing distorted CuCl4(OH)2 octahedra. Two Tl3+ cations occupy the centre of isolated TlCl6 and TlCl4(H2O)2 octahedra connected to each other and to the Cu polyhedral layers via KCl6 and KCl9 polyhedra. The name reflects the bright golden-yellow colour of the mineral (from the Greek χρυσός, gold) and the presence of thallium. Chrysothallite is the second known mineral with species-defining trivalent thallium.

New arsenate minerals from the Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. VI. Melanarsite, K3Cu7Fe3+O4(AsO4)4

Abstract The newmineralmelanarsite,K3Cu7Fe3+O4(AsO4)4,was found in the sublimates of theArsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka Peninsula, Russia. It is associated with dmisokolovite, shchurovskyite, bradaczekite, hematite, tenorite, aphthitalite, johillerite, arsmirandite, As-bearing orthoclase, hatertite, pharmazincite, etc. Melanarsite occurs as tabular to prismatic crystals up to 0.4 mm, separate or combined in clusters up to 1 mm across or in interrupted crusts up to 0.02 cm× 1 cm× 1 cm covering basalt scoria. The mineral is opaque, black, with a vitreous lustre. Melanarsite is brittle.Mohs’ hardness is ~4 and the mean VHN = 203 kg mm-2. Cleavage was not observed and the fracture is uneven. Dcalc is 4.39 g cm-3. In reflected light, melanarsite is dark grey. Bireflectance is weak, anisotropism is very weak. Reflectance values [R1-R2, % (λ, nm)] are 10.5- 9.4 (470), 10.0-8.9 (546), 9.7-8.7 (589), 9.5-8.6 (650). The Raman spectrum is reported. Chemical composition (wt.%, electron microprobe) is K2O 10.70, CaO 0.03, CuO 45.11, ZnO 0.24, Al2O3 0.32, Fe2O3 6.11, TiO2 0.12, P2O5 0.07, As2O5 36.86, total 99.56. The empirical formula, based on 20 O apfu, is (K2.81Ca0.01)Σ2.82(Cu7.02Fe3+0.95Al0.08Zn0.04Ti0.02)Σ8.11(As3.97P0.01)Σ3.98O20. Melanarsite is monoclinic, C2/c, a = 11.4763(9), b = 16.620(2), c = 10.1322(8) Å, β = 105.078(9)°, V = 1866.0(3) Å3 and Z = 4. The strongest reflections of the powder X-ray diffraction pattern [d,Å(I)(hkl)] are 9.22(100)(110), 7.59(35)(1̄11), 6.084(17) (111), 4.595(26)(1̄31, 220, 2̄21), 3.124(22)(3̄31,1̄51), 2.763(20)(400, 1̄52), 2.570(23)(043) and 2.473(16) (260, 2̄61, 350). Melanarsite has a novel structure type. Its crystal structure, solved from single-crystal X-ray diffraction data (R = 0.091), is based upon a heteropolyhedral pseudo-framework built by distortedCu(1-3)O6 and (Fe,Cu)O6 octahedra and As(1-3)O4 tetrahedra. Two crystallographically independent K+ cations are located in the tunnels and voids of the pseudo-framework centring eight- and seven-fold polyhedra. The name reflects the mineral being an arsenate and its black colour (from the Greek μέλαν, black).

Large-volume platinum ore deposits in zonal mafic-ultramafic complexes of the Ural-Alaskan type and the outlook for their development

The results of mineralogical-technological studies of PGM mineralization in zonal mafic-ultramafic complexes of the Ural-Alaskan type are given. All studied massifs in the Urals and Kamchatka are characterized by similar evolution of mineral assemblages. The chromite (platinum-chromitite-dunite) and dunite (platinum-pegmatoid dunite) geological-economic types of small platinum deposits and occurrences are separate enriched sites (ore shoots) of large-volume platinum ore deposits. These are rather thick and extended zones of recrystallized dunites with attributes of high-temperature structural deformations and intense fluid reworking. Low Pt grade in ore (<0.5 gpt) is determined by fine and very fine (grain size class — 80 μm) euhedral PGM crystals distributed rather uniformly in ore mass. The high and occasionally anomalous Pt contents (up to 1 kgpt and higher) are related to large xenomorphic segregations of PGM, which concentrate largely in the marginal parts of separate chromite segregations. The significant part of productive Pt-bearing mineralization is hosted in olivine matrix of igneous rocks, so that recovery of platinum cannot be associated only with separation of chromite ore. The direct gravity concentration of platinum ore without preliminary separation of chromite concentrate is recommended as the main technique of platinum recovery. The technological scheme provides for two-stage comminution of ore with between-cycle separation of coarse the PGM fraction into the concentrate as a commodity product. The results obtained allow us to regard the aforementioned mineralization as a new geological and economic type of lode platinum deposits, whose potential is comparable with active platinum reserves in the complex Cu-Ni ores of the Noril’sk district.

New arsenate minerals from the Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. VII. Pharmazincite, KZnAsO4

Abstract The new mineral pharmazincite, KZnAsO4, 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 closely associated with shchurovskyite, dmisokolovite, bradaczekite, arsmirandite, tilasite, johillerite, tenorite, hematite, aphthitalite and As-bearing orthoclase. Pharmazincite occurs as prismatic to acicular crystals up to 1 mmlong and up to 0.03 mmthick typically combined in near-parallel, radial or chaotic intergrowths, open-work aggregates or crusts up to 2 mm across. Pharmazincite is colourless to white, transparent, with a vitreous lustre. It is brittle, with a stepped fracture and a perfect cleavage parallel to [001]. Dcalc is 4.75 g cm-3. Pharmazincite is optically uniaxial (-), ω = 1.649(2), ε = 1.642(2). The Raman spectrum is reported. The chemical composition (wt.%, electron-microprobe data) is: K2O 18.98, CaO 0.14, MgO 1.20, CuO 4.41, ZnO 27.58, Fe2O3 0.15, P2O5 0.50, As2O5 46.67, total 99.63. The empirical formula, calculated based on 4 O apfu, is: (K0.97Ca0.01)Σ0.98(Zn0.82Cu0.13Mg0.07Fe3+0.01)Σ1.03(As0.98P0.02)Σ1.00O4. The strongest reflections of the powder X-ray diffraction pattern [d,Å(I )(hkl)] are: 6.36 (28)(111), 4.64(45)(220), 4.35(48)(002), 3.260(36)(411), 3.179(100)(222), 2.770(26)(113), 2.676(77) (600), 2.278(15)(602) and 1.710(15)(713, 115). Pharmazincite is hexagonal, a = 18.501(4), c = 8.7114(9) Å, V = 2582.4(8) Å3 and Z = 24 (single-crystal XRD data). Its space group is P63, by analogy with synthetic KZnAsO4 that has a crystal structure based upon a tetrahedral tridymite-type {ZnAsO4}- framework. It is isostructural with megakalsilite KAlSiO4. The new mineral is named for its chemical constituents.