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Keplerite is a new mineral, the Ca-dominant counterpart of the most abundant meteoritic phosphate, which is merrillite. The isomorphous series merrillite-keplerite, Ca9NaMg(PO4)7-Ca9(Ca0.5☐0.5) Mg(PO4)7, represents the main reservoir of phosphate phosphorus in the solar system. Both minerals are related by the heterovalent substitution at the B-site of the crystal structure: 2Na+ (merrillite) → Ca2+ + ☐ (keplerite). The near-end-member keplerite of meteoritic origin occurs in the main-group pallasites and angrites. The detailed description of the mineral is made based on the Na-free type material from the Marjalahti meteorite (the main group pallasite). Terrestrial keplerite was discovered in the pyrometamorphic rocks of the Hatrurim Basin in the northern part of Negev desert, Israel. Keplerite grains in Marjalahti have an ovoidal to cloudy shape and reach 50 μm in size. The mineral is colorless, transparent with a vitreous luster. Cleavage was not observed. In transmitted light, keplerite is colorless and non-pleochroic. Uniaxial (−), ω = 1.622(1), ε = 1.619(1). Chemical composition (electron microprobe, wt%): CaO 48.84; MgO 3.90; FeO 1.33; P2O5 46.34, total 100.34. The empirical formula (O = 28 apfu) is Ca9.00(Ca0.33Fe0.202+☐0.47)1.00Mg1.04P6.97O28. The ideal formula is Ca9(Ca0.5☐0.5)Mg(PO4)7. Keplerite is trigonal, space group R3c, unit-cell parameters refined from single-crystal data are: a = 10.3330(4), c = 37.0668(24) Å, V = 3427.4(3) Å3, Z = 6. The calculated density is 3.122 g/cm−3. The crystal structure has been solved and refined to R1 = 0.039 based on 1577 unique observed reflections [I>2σ(I)]. A characteristic structural feature of keplerite is a partial (half-vacant) occupancy of the sixfold-coordinated B-site (denoted as CaIIA in the earlier works). The disorder caused by this cation vacancy is the most likely reason for the visually resolved splitting of the ν1 (symmetric stretching) (PO4) vibration mode in the Raman spectrum of keplerite. The mineral is an indicator of high-temperature environments characterized by extreme depletion of Na. The association of keplerite with “REE-merrillite” and stanfieldite provides evidence for the similarity of temperature conditions that occurred in the Mottled Zone to those expected during the formation of pallasite meteorites and lunar rocks. Because of the cosmochemical significance of the merrillite-keplerite series and by analogy to plagioclases, the Na-number measure, 100×Na/(Na+Ca) (apfu), is herein proposed for the characterization of solid solutions between merrillite and keplerite. The merrillite end-member, Ca9NaMg(PO4)7, has the Na-number = 10, whereas keplerite, Ca9(Ca0.5☐0.5)Mg(PO4)7, has Na-number = 0. Keplerite (IMA 2019-108) is named in honor of Johannes Kepler (1571–1630), a prominent German naturalist, for his contributions to astronomy and crystallography.

The new wermlandite-group mineral erssonite, ideally CaMg7Fe3+2(OH)18(SO4)2⋅12H2O (or [Mg7Fe3+2(OH)18][Ca(SO4)2]⋅12H2O), was discovered in a late-stage, low-temperature assemblage in cavities of a magnetite-bearing dolomitic rock from the Långban deposit, Värmland county, Bergslagen ore province, Sweden. The associated minerals are dolomite, calcite, members of the magnetite–magnesioferrite solid-solution series, phlogopite, chrysotile, pyroaurite and norbergite. Erssonite has a vitreous lustre and forms colourless, platy hexagonal crystals flattened on [0001], up to 0.5 mm across and up to 10 μm thick, occurring mainly as aggregates in cavities of dolomitic rock. Erssonite is malleable; separate crystals are flexible and non-elastic, with a perfect, mica-like cleavage on {0001}. The calculated density is equal to 2.02 g⋅cm–3. Raman spectroscopy shows the presence of typical bands for S–O bonds attributed to intercalated SO42– anions and structural OH– anions together with the absence of C–O bonds, attributed to carbonate anions. The chemical composition is (wt.%, electron microprobe, H2O content is calculated from structure data): MgO 28.67, CaO 2.76, Al2O3 0.23, Cr2O3 0.23, Fe2O3 16.00, SiO2 0.48, SO3 14.80, H2O 35.58, total 98.75. The empirical formula based on 38 O atoms is H41.48Ca0.52Mg7.47Fe3+2.11Al0.05Cr0.03S1.94Si0.08O38. The ideal formula is CaMg7Fe3+2(OH)18(SO4)2⋅12H2O or {Mg7Fe3+2(OH)18}{[Ca(H2O)6](SO4)2(H2O)6}. The crystal structure was determined using single-crystal X-ray diffraction data and refined to R = 0.093. Erssonite is trigonal, P$\bar{3}$c1, with a = 9.3550(6), c = 22.5462(14) Å, V = 1708.8(2) Å3 and Z = 2. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %)(hkl)] are: 11.22 (90)(002), 5.63 (64)(004), 4.670 (100)(110, 104, 014), 2.626 (64)(032, 302), 2.435 (66)(034, 304) and 1.951 (45)(038, 308). The mineral is named in honour of the Swedish amateur mineralogist Dr. Anders Ersson (b. 1971).

Schreibersite, (Fe,Ni)3P, the most abundant cosmic phosphide, is a principal carrier of phosphorus in the natural Fe-Ni-P system and a likely precursor for prebiotic organophosphorus compounds at the early stages of Earth’s evolution. The crystal structure of the mineral contains three metal sites allowing for unrestricted substitution of Fe for Ni. The distribution of these elements across the structure could serve as a tracer of crystallization conditions of schreibersite and its parent celestial bodies. However, discrimination between Fe (Z = 26) and Ni (Z = 28) based on the conventional X-ray structural analysis was for a long time hampered due to the proximity of their atomic scattering factors. We herein show that this problem has been overcome with the implementation of area detectors in the practice of X-ray diffraction. We report on previously unknown site-specific substitution trends in schreibersite structure. The composition of the studied mineral encompasses a Ni content ranging between 0.03 and 1.54 Ni atoms per formula unit (apfu): the entire Fe-dominant side of the join Fe3P-Ni3P. Of 23 schreibersite crystals studied, 22 comprise magmatic and non-magmatic iron meteorites and main group pallasites. The near end-member mineral (0.03 Ni apfu) comes from the pyrometamorphic rocks of the Hatrurim Basin, Negev desert, Israel. It was found that Fe/Ni substitution in schreibersite follows the same trends in all studied meteorites. The dependencies are nonlinear and can be described by second-order polynomials. However, the substitution over the M2 and M3 sites within the most common range of compositions (0.6 < Ni

Three new isostructural minerals, alexkuznetsovite-(La), ideally La2Mn(CO3)(Si2O7), alexkuznetsovite-(Ce) Ce2Mn(CO3)(Si2O7) and biraite-(La) La2Fe2+(CO3)(Si2O7), were discovered in polymineralic nodules from the Mochalin Log REE deposit, South Urals, Russia. The new minerals form anhedral grains up to 0.3 mm × 0.4 mm [alexkuznetsovite-(La)], 0.5 mm × 0.9 mm [alexkuznetsovite-(Ce)] and 0.2 mm × 1.2 mm [biraite-(La)] embedded in granular aggregates consisting of different REE minerals [allanite-(Ce)/-(La), bastnäsite-(Ce)/-(La), fluorbritholite-(Ce), perbøeite-(Ce)/-(La), percleveite-(Ce)/-(La) and törnebohmite-(Ce)/-(La)]. All three new species are brown to dark brown, translucent in thin fragments, with white streak, vitreous lustre and Mohs’ hardness of ~5. Dcalc = 4.713 [alexkuznetsovite-(La)], 4.687 [alexkuznetsovite-(Ce)] and 4.682 [biraite-La)] g⋅cm–3. Their empirical formulae, calculated on the basis of 2 Si and 10 O apfu, are: alexkuznetsovite-(La): (La0.98Ce0.89Nd0.10Pr0.05)Σ2.02Mn2+0.50Fe2+0.29Ca0.12Mg0.03(CO3)0.94(HCO3)0.06 (Si2O7); alexkuznetsovite-(Ce): (Ce0.96La0.78Nd0.16Pr0.07)Σ1.97Th0.01Mn2+0.50Fe2+0.33Ca0.14Mg0.02(CO3)0.93(HCO3)0.07(Si2O7); and biraite-(La): (La0.95Ce0.87Nd0.08Pr0.04)Σ1.94Th0.01Ca0.12Fe2+0.44Mn2+0.38Mg0.07(CO3)0.88(HCO3)0.12(Si2O7). The new minerals are monoclinic, P21/c and Z = 4. The unit-cell parameters of alexkuznetsovite-(La)/alexkuznetsovite-(Ce)/biraite-(La) are: a = 6.5642(3)/6.5764(4)/6.5660(10), b = 6.7689(3)/6.7685(4)/6.7666(11), c = 18.7213(10)/18.7493(15)/18.698(3) Å, β = 108.684(6)/108.672(8)/108.952(16)° and V = 788.00(7)/790.66(10)/785.7(2) Å3. The crystal structures are solved from single-crystal X-ray diffraction data; R = 0.0628 [alexkuznetsovite-(La)], 0.0589 [alexkuznetsovite-(Ce)] and 0.1193 [biraite-(La)]. A new biraite group is defined; it includes isostructural biraite-(Ce) and the three new minerals described herein. The rootname alexkuznetsovite is given in honour of the Russian mineral collector Alexey M. Kuznetsov (born 1962) who provided samples in which all three new minerals were found. The Levinson's suffix-modifier -(La) or -(Ce) indicates the predominance of La or Ce among REE in the mineral. Biraite-(La) is named as an analogue of biraite-(Ce) with La prevailing among REE.

Six different exsolution types are found in crystals of aphthitalite-group alkali sulfates from exhalations of the active Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. The coexisting minerals in these exsolutions are metathénardite, ideally Na2SO4 (P63/mmc), and vanthoffite, Na6Mg(SO4)4 (P21/c) (Type I); metathénardite and belomarinaite, KNaSO4 (P3m1) (Type II); thénardite, Na2SO4 (Fddd), and aphthitalite, K3Na(SO4)2 (Pm1) (Type III); aphthitalite and arcanite, K2SO4 (Pnma) (Type IV); metathénardite and natroaphthitalite, KNa3(SO4)2 (Pm1) (Type V); and two chemical varieties of metathénardite (Type VI). The exsolution processes occur in crystals belonging to the high-temperature, hexagonal Na2SO4(I) (= metathénardite, P63/mmc) structure type with different K:Na ratios formed at temperatures higher than 500 °C. The similarity and hexagonal close-packed nature of the crystal structures of the coexisting phases, all representatives of aphthitalite-like structure types, cause the coherent conjugation of domains during diffusion and cation ordering in the parent phase. The breakdown of solid solution can be facilitated by the mosaic character of crystals of a parent phase (incoherent grain boundaries) and the presence of coherent twin boundaries. The heating of samples with exsolution Types II and V up to 700 °C over 24 h shows that diffusion of K and Na through the domain borders does not result in the complete disorder of these cations and the extinction of domains with different crystal structures.

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).

Cyclophosphates are a class of energy-rich compounds whose hydrolytic decomposition (ring opening) liberates energy that is sufficient for initiation of biomimetic phosphorylation reactions. Because of that, cyclophosphates might be considered as a likely source of reactive prebiotic phosphorus on early Earth. A major obstacle toward adoption of this hypothesis is that cyclophosphates have so far not been encountered in nature. We herein report on the discovery of these minerals in the terrestrial environment, at the Dead Sea basin in Israel. Cyclophosphates represent the most condensed phosphate species known in nature. A pathway for cyclophosphate geosynthesis is herein proposed, involving simple pyrolytic oxidation of terrestrial phosphides. Discovery of natural cyclophosphates opens new opportunities for modeling prebiotic phosphorylation reactions that resulted in the emergence of primordial life on our planet.

The new ettringite-group mineral chiyokoite, ideally Ca3Si(CO3)[B(OH)4]O(OH)5·12H2O, was found in a hydrothermally altered calc-silicate skarn at the Fuka mine, Okayama Prefecture, Japan. Associated minerals are calcite, henmilite, and tacharanite. Chiyokoite occurs as hexagonal prismatic crystals up to 30 μm long and up to 20 μm thick. The major forms are the hexagonal prism {100} and monohedra {0001} and {000}. The crystals are combined in clusters which form friable nests up to 1 cm across. The mineral is pink to colorless with white streak and vitreous luster. The cleavage is parallel to {100} and {0001}, good. The fracture is stepped. Dmeas is 1.85(1) g/cm3, Dcalc is 1.85 g/cm3. Chiyokoite is optically uniaxial (–), ω = 1.523(2) and ε = 1.492(3) (589 nm). The infrared spectrum is reported. The chemical composition (wt.%) is CaO 27.56, B2O3 3.47, Al2O3 3.05, Fe2O3 0.12, As2O3 4.77, MnO2 0.32, SiO2 6.55, SO3 0.76, H2O 46.3, CO2 7.30, total 100.2. The empirical formula calculated on the basis of 3 Ca apfu is H31.37Ca3(Si0.67Al0.37Mn4+0.02Fe3+0.01)Σ1.07(C1.01B0.61As3+0.29S0.06)Σ1.97O24.19. The simplified general formula is Ca3(Si,Al)(CO3,AsO3)[B(OH)4,AsO3](OH)6·12H2O. Chiyokoite is hexagonal, P63, a = 11.0119(5), c = 10.5252(6) Å, and V = 1105.3(1) Å3. The strongest reflections of the powder X-ray diffraction pattern [d,Å(I)(hkl)] are: 9.53(100)(100), 5.50(24)(110), 4.618(11)(102), 3.812(23)(112), 3.412(15)(211), 2.726(14)(302), 2.521(19)(123), and 2.172(13)(320,402,223). The crystal structure, refined from single-crystal X-ray diffraction data [R1(F) = 0.042], is based on [Ca3(Si,Al)(OH)6(H2O)12] columns parallel to the c axis with B(OH)4– and CO32– and admixed AsO33– anionic groups in channels between the columns. The mineral is named in honor of Professor Chiyoko Henmi (1949–2018).

Two new isostructural minerals radekškodaite-(La) (CaLa5)(Al4Fe2+)[Si2O7][SiO4]5O(OH)3 and radekškodaite-(Ce) (CaCe5)(Al4Fe2+)[Si2O7][SiO4]5O(OH)3 were discovered in polymineralic nodules from the Mochalin Log REE deposit, South Urals, Russia. Radekškodaite-(La) is associated with allanite-(Ce), allanite-(La), bastnäsite-(Ce), bastnäsite-(La), ferriallanite-(Ce), ferriallanite-(La), ferriperbøeite-(La), fluorbritholite-(Ce), törnebohmite-(Ce) and törnebohmite-(La). Radekškodaite-(Ce) is associated with ancylite-(Ce), bastnäsite-(Ce), bastnäsite-(La), lanthanite-(La), perbøeite-(Ce) and törnebohmite-(Ce). The new minerals form isolated anhedral grains up to 0.35 × 0.75 mm [radekškodaite-(La)] and 1 mm × 2 mm [radekškodaite-(Ce)]. Both minerals are greenish-brown with vitreous lustre. Dcalc = 4.644 [radekškodaite-(La)] and 4.651 [radekškodaite-(Ce)] g cm–3. Both minerals are optically biaxial (+); radekškodaite-(La): α = 1.790(7), β = 1.798(5), γ = 1.825(8) and 2Vmeas = 60(10)°; radekškodaite-(Ce): α = 1.798(6), β = 1.806(6), γ = 1.833(8) and 2Vmeas = 65(10)°. Chemical data [wt.%, electron-microprobe; FeO:Fe2O3 by charge balance; H2O by stochiometry; radekškodaite-(La)/radekškodaite-(Ce)] are: CaO 3.40/2.74, La2O3 27.68/22.23, Ce2O3 20.39/24.30, Pr2O3 0.94/1.48, Nd2O3 1.71/3.18, ThO2 0.23/0.24, MgO 0.85/1.04, Al2O3 10.35/10.84, MnO 0.64/0.69, FeO 2.55/2.76, Fe2O3 3.12/2.57, TiO2 0.13/0.04, SiO2 26.03/26.10, F 0.10/0.09, H2O 1.62/1.63, –O=F –0.04/–0.04, total 99.70/99.89. The empirical formulae based on O28(OH,F)3 are: radekškodaite-(La): (Ca0.98Th0.01La2.75Ce2.01Nd0.16Pr0.09)Σ6.00(Al3.28Fe3+0.63Fe2+0.57Mg0.34Mn0.15Ti0.03)Σ5.00Si7.00O28[(OH)2.91F0.09]; radekškodaite-(Ce): (Ca0.79Mn0.16Th0.01Ce2.39La2.20Nd0.30Pr0.14)Σ5.99(Al3.43Fe2+0.62Fe3+0.52Mg0.42Ti0.01)Σ5.00Si7.00O28[(OH)2.92F0.08]. Both minerals are monoclinic, P21/m; the unit-cell parameters [radekškodaite-(La)/radekškodaite-(Ce)] are: a = 8.9604(3)/8.9702(4), b = 5.7268(2)/5.7044(2), c = 25.1128(10)/25.1642(13) Å, β = 116.627(5)/116.766(6)°, V = 1151.98(7)/1149.68(11) Å3 and Z = 2/2. The crystal structures are solved based on single-crystal X-ray diffraction data; R = 0.0554 [radekškodaite-(La)] and 0.0769 [radekškodaite-(Ce)]. Both minerals belong to the epidote–törnebohmite polysomatic series and represent first members of ET2-type: their structure consists of regular alternating modules, one slab of the epidote (E) structure and two slabs of törnebohmite (T). The rootname radekškodaite is given in honor of the Czech mineralogist Radek Škoda (born 1979), Associate Professor at Masaryk University, Brno, Czech Republic. The suffix-modifier -(La) or -(Ce) indicates the predominance of La or Ce among REE in the mineral.

The new leucophosphite-group mineral ammoniotinsleyite is found in a guano deposit located on the Pabellón de Pica Mountain, Iquique Province, Tarapacá Region, Chile. Associated minerals are halite, gypsum, salammoniac and clay minerals. Ammoniotinsleyite occurs as pink to pale violet globular aggregates up to 3 mm across with individual single crystals ~10–15 μm. The mineral is brittle. Its Mohs hardness is 4. Dmeas. = 2.42(2) g cm–3 and Dcalc. = 2.451 g cm–3. The IR spectrum shows the presence of NH4+ and PO43– groups and H2O molecules. Ammoniotinsleyite is optically biaxial (+), α = 1.557(2), β = 1.559 (calc.), γ = 1.563(2) (λ = 589 nm); and 2Vmeas. = 75(10)°. The chemical composition (K, Mg, Ca, Al, Fe and P from electron-microprobe data; H, C and N measured by gas chromatography on products of ignition at 1200°C; wt.%) is: (NH4)2O 7.25, K2O 1.50, MgO 0.42, CaO 0.34, Al2O3 29.91, Fe2O3 2.36, P2O5 43.97, H2O 14.89, CO2 below detection limit, total 100.64. The empirical formula is [(NH4)0.88K0.10Ca0.02)]Σ1.00(Al1.86Fe3+0.09Mg0.03)Σ1.98(PO4)1.96(OH)1.05⋅2.11H2O. The idealised formula is (NH4)2Al2(PO4)2(OH)⋅2H2O. The crystal structure of ammoniotinsleyite was refined based on powder X-ray diffraction data, using the Rietveld method. The final agreement factors are: Rp = 0.0071, Rwp = 0.0093 and Robs = 0.0167. The new mineral is isostructural with tinsleyite, spheniscidite and leucophosphite. It is monoclinic, space group P21/n, a = 9.5871(1) Å, b = 9.6089(1) Å, c = 9.6467(2) Å, β = 103.4461(8)°, V = 864.31(2) Å3 and Z = 4. The strongest reflections of the powder X-ray diffraction pattern [d,Å(I,%)(hkl)] are: 7.56(23)($\bar{1}$01), 6.71(79)(011, 110), 5.947(100)(101, $\bar{1}$11), 4.676(36)(002, 200), 3.032(28)($\bar{1}$13, 031, 130), 2.958(25)($\bar{2}$22, 310, $\bar{1}$31) and 2.635(29)($\bar{2}$31).

The new mineral kainotropite Cu4Fe3+O2(V2O7)(VO4) was found in sublimates of fumaroles related to the Tolbachik volcano, Kamchatka, Russia. The holotype specimen originates from the Yadovitaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption; associated minerals are hematite, langbeinite, calciolangbeinite, tenorite, piypite, lyonsite, rutile, pseudobrookite, sanidine, and lammerite. In paleo-fumarolic deposits of Mountain 1004 kainotropite is associated with diopside and hematite. It forms prismatic crystals up to 0.2 × 0.2 × 0.5 mm3, isolated or combined in clusters up to 0.7 mm across. Kainotropite is iron-black to reddish-black, with semi-metallic luster. Dcalc is 4.10 g/cm3. In reflected light, kainotropite is grey, weakly anisotropic. The reflectance values [Rmax–Rmin,% (λ, nm)] are: 18.3–17.3 (470), 17.3–16.3 (546), 16.9–15.7 (589), 16.3–15.1 (650). The chemical composition of the holotype sample (wt.%, electron microprobe) is: CuO 46.69, Al2O3 1.40, Fe2O3 10.04, TiO2 0.32, V2O5 37.58, As2O5 2.55, MoO3 0.76, total 99.34. The empirical formula, based on 13 O apfu, is: Cu3.96Fe3+0.85Al0.19Ti0.03(V2.78As0.15Mo0.04)Σ2.97O13. Kainotropite is orthorhombic, Pnma, a = 14.139(2), b = 6.7102(7), c = 11.4177(15) Å, V = 1083.3(2) Å3, and Z = 4. The strongest reflections of the powder XRD pattern [d,Å(I)(hkl)] are: 8.89(100)(101), 5.728(33)(002), 3.698(35)(212), 3.357(52)(020,203), 3.034(77)(220), 2.968(60)(303), and 2.655(27)(321,204). The crystal structure was solved from single-crystal XRD data, R = 0.085. Kainotropite represents a novel structure type. Cu2+ polyhedra (distorted tetragonal pyramids and strongly distorted octahedra) and Fe3+ octahedra are connected via common edges to form zigzag ribbons. Adjacent ribbons are connected by both V2O7 and VO4 groups (isolated from each other) to form a heteropolyhedral pseudo-framework. The name kainotropite is derived from the Greek word καινóτρoπoς, unusual, in allusion to its uncommon (for natural vanadates) anionic composition: it is the first mineral containing both pyrovanadate (V2O7)4– and orthovanadate (VO4)3– anions.

This paper is a first detailed report of natural hexagonal solid solutions along the join Fe2P–Ni2P. Transjordanite, Ni2P, a Ni-dominant counterpart of barringerite (a low-pressure polymorph of Fe2P), is a new mineral. It was discovered in the pyrometamorphic phosphide assemblages of the Hatrurim Formation (the Dead Sea area, Southern Levant) and was named for the occurrence on the Transjordan Plateau, West Jordan. Later on, the mineral was confirmed in the Cambria meteorite (iron ungrouped, fine octahedrite), and it likely occurs in CM2 carbonaceous chondrites (Mighei group). Under reflected light, transjordanite is white with a beige tint. It is non-pleochroic and weakly anisotropic. Reflectance values for four COM recommended wavelengths are [Rmax/Rmin, % (λ, nm)]: 45.1/44.2 (470), 49.9/48.5 (546), 52.1/50.3 (589), 54.3/52.1 (650). Transjordanite is hexagonal, space group P62m; unit-cell parameters for the holotype specimen, (Ni1.72Fe0.27)1.99P1.02, are: a = 5.8897(3), c = 3.3547(2) Å, V = 100.78(1) Å3, Z = 3. Dcalc = 7.30 g/cm3. The crystal structure of holotype transjordanite was solved and refined to R1 = 0.013 based on 190 independent observed [I > 2σ(I)] reflections. The crystal structure represents a framework composed of two types of infinite rods propagated along the c-axis: (1) edge-sharing tetrahedra [M(1)P4] and (2) edge-sharing [M(2)P5] square pyramids. Determination of unit-cell parameters for 12 members of the Fe2P–Ni2P solid-solution series demonstrates that substitution of Ni for Fe in transjordanite and vice versa in barringerite does not obey Vegard’s law, indicative of preferential incorporation of minor substituent into M(1) position. Terrestrial transjordanite may contain up to 3 wt% Mo, whereas meteoritic mineral bears up to 0.2 wt% S.

Natroaphthitalite K(Na,K)2Na(SO4)2, a new aphthitalite-group mineral, was found in exhalations of the active Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka Peninsula, Russia. The associated minerals are anhydrite, langbeinite, hematite, tenorite, sanidine, johillerite, tilasite, and belomarinaite. Natroaphthitalite occurs as translucent yellow to colorless roundish single-crystal individuals up to 1 cm in diameter, sometimes combined in crusts up to 2 cm across, and as aqua-transparent colorless tabular to lamellar hexagonal crystals up to 2 mm across, sometimes skeletal, typically combined in parallel intergrowths or brush-like aggregates. Dcalc is 2.664 g/cm3. Natroaphthitalite is optically uniaxial (+), ω = 1.488(2), ε = 1.490(2). The chemical composition (wt.%, electron microprobe) is: Na2O 22.54, K2O 26.39, SO3 51.78, total 100.71. The empirical formula calculated based on 8 O apfu is K1.735Na2.252S2.002O8 (average of 15 spot analyses). The crystal structures of natroaphthitalite and the associated aphthitalite-group mineral belomarinaite, ideally KNaSO4, from the Arsenatnaya fumarole were solved using single-crystal X-ray diffraction and refined to R1 = 0.0283 and 0.0261, respectively. The unit-cell parameters, Z, and space groups are a = 5.6014(3), c = 7.1507(5) Å, V = 194.30(2) Å3, Z = 1, and for natroaphthitalite and a = 5.6088(3), c = 7.1858(4) Å, V = 195.77(1) Å3, Z = 2, and P3m1 for belomarinaite. The crystal chemical formulae of natroaphthitalite and belomarinaite (Z = 1) are XK1.00Y(Na1.28K0.72)Σ2.00MNa1.00(TSO4)2 and XK1.00Y1(Na0.96K0.04)Σ1.00Y2(K0.94Na0.06)Σ1.00MNa1.00(TSO4)2, respectively. Natroaphthitalite is isostructural with aphthitalite K3Na(SO4)2 = XKYK2MNa(TSO4)2 (both have centrosymmetric structures) with prevailing Na over K at the Y site of the crystal structure. Belomarinaite XKY2KY1NaMNa(TSO4)2 is the fully cation-ordered species, with acentric structure, in the series of natural aphthitalite-like K-Na sulfates.

Negevite, ideally NiP2, is a new phosphide mineral from pyrometamorphic complex of the Hatrurim Formation (the Mottled Zone), Southern Levant. It is found in phosphide assemblages of the Hatrurim Basin, south Negev Desert, Israel, and Daba-Siwaqa complex, Jordan. The mineral occurs as tiny isometric grains reaching 15 μm in size and forms intimate intergrowths with other phosphides related to the Fe-Ni-P system. In reflected light, negevite is white with yellowish tint and isotropic. Reflectance values for COM recommended wavelengths [R (%), λ (nm)] are as follows: 54.6 (470), 55.0 (546), 55.3 (589), 55.6 (650). Chemical composition of the holotype specimen (electron micro-probe, wt%): Ni 42.57, Co 3.40, Fe 2.87, P 42.93, S 8.33, total 100.10, corresponding to the empirical formula (Ni0.88Co0.07Fe0.06)Σ1.01(P1.68S0.31)Σ1.99. The crystal structure of negevite was solved and refined to R1 = 1.73% based on 52 independent observed [I >2σ(I)] reflections. The mineral is cubic, space group Pa3, a = 5.4816(5) Å, V = 164.71(3) Å3, and Z = 4. Dx = 4.881(1) g/cm3 calculated on the basis of the empirical formula. Negevite is a first natural phosphide belonging to the pyrite structure type. It is a chemical and structural analog of vaesite, NiS2, krutovite, NiAs2, and penroseite, NiSe2. The well-explored catalytic and photocatalytic properties of a synthetic counterpart of negevite could provide new insights into the possible role of higher phosphides as a source of low-valent phosphorus in prebiotic phosphorylation processes.

Experimental investigations of crystallization in a family of uranyl triacetate compounds with Na, K, Rb and Cs were performed. The crystal structures of two novel Cs- and Rb-bearing tri(acetato)uranylates were solved, and the content of H2O molecules in the crystal structure of K-bearing uranyl triacetate was refined. Synthesized compounds were analyzed using IR spectroscopy and single-crystal X-ray diffraction. Crystal chemical analysis of the M[(UO2)(CH3COO)3](H2O) n family (M = Na, K, Rb, Cs; n = 0–1.0) reveals the sequence of structural transformations depending on the size of alkali cation resulting in the symmetry reduction from cubic P 213 (for Na), through tetragonal I 41/a (for K and Rb) to triclinic P 1̅ space groups (for Cs), which is in accordance with the principle of morphotropism, suggested by Paul von Groth, founder of the Zeitschrift für Krystallographie journal, in 1870.

This is the initial paper in a pair of articles devoted to silicate minerals from fumaroles of the Tolbachik volcano (Kamchatka, Russia). These papers contain the first systematic data on silicate mineralization of fumarolic genesis. In this article nesosilicates (forsterite, andradite and titanite), cyclosilicate (a Cu,Zn-rich analogue of roedderite), inosilicates (enstatite, clinoenstatite, diopside, aegirine, aegirine-augite, esseneite, “Cu,Mg-pyroxene”, wollastonite, potassic-fluoro-magnesio-arfvedsonite, potassic-fluoro-richterite and litidionite) and phyllosilicates (fluorophlogopite, yanzhuminite, “fluoreastonite” and the Sn analogue of dalyite) are characterized with a focus on chemistry, crystal-chemical features and occurrence. Unusual As5+-rich varieties of forsterite, andradite, titanite, pyroxenes, amphiboles and mica are described. General data on silicate-bearing active fumaroles and the diversity and distribution of silicates in fumarole deposits are reported. Evidence for the fumarolic origin of silicate mineralization is discussed.

This second of two companion articles devoted to silicate mineralization in fumaroles of the Tolbachik volcano (Kamchatka, Russia) reports data on chemistry, crystal chemistry and occurrence of tectosilicates: sanidine, anorthoclase, ferrisanidine, albite, anorthite, barium feldspar, leucite, nepheline, kalsilite, sodalite and hauyne. Chemical and genetic features of fumarolic silicates are also summarized and discussed. These minerals are typically enriched with “ore” elements (As, Cu, Zn, Sn, Mo, W). Significant admixture of As5+ (up to 36 wt % As2O5 in sanidine) substituting Si is the most characteristic. Hauyne contains up to 4.2 wt % MoO3 and up to 1.7 wt % WO3. All studied silicates are hydrogen-free, including mica and amphiboles which are F-rich. Iron-bearing minerals contain only Fe3+ due to strongly oxidizing formation conditions. In Tolbachik fumaroles, silicates were formed in the temperature range 500–800 ∘C as a result of direct deposition from the gas phase (as volcanic sublimates) or gas–rock interactions. The zonation in distribution of major silicate minerals observed in a vertical section of the Arsenatnaya fumarole, from deep (the hottest) to upper parts is diopside + forsterite + enstatite + andradite → diopside → fluorophlogopite + diopside → sanidine + fluorophlogopite → sanidine. This is in agreement with volatilities of major species-defining metals in volcanic gases. From a crystal-chemical viewpoint, this series corresponds to the following sequence of crystallization of minerals with temperature decrease: nesosilicates → inosilicates → phyllosilicates → tectosilicates.

This paper describes specific features of isomorphism of unusual amphiboles containing up to 23 wt% ZnO and up to 1.3 wt% CuO from sulfide-free metasomatic rocks of the “Mixed Series” metamorphic complex, Pelagonian Massif, Republic of North Macedonia, in which chalcophile elements (Pb, Cu, Zn, Sb, As) occur in high concentrations in the form of oxides and oxysalts. The studied amphiboles belong to six mineral species: magnesio-riebeckite, ferri-winchite, F-dominant analogue of ferri-winchite (“ferri-fluoro-winchite”), ferri-barroisite, ferri-nyboite, and a zinc-rich amphibole related to clino-suenoite. The main substitution schemes are Zn → Mg and Na + Fe3+ → Ca + Mg. The amphibole related to clino-suenoite has been studied in the most detailed way. Its empirical formula is (Mg2.99Zn2.47Mn1.26Fe3+0.30Ca0.07)Σ7.09(Si7.89Fe3+0.06Al0.05O22)(OH)2, and it is the most Zn-rich amphibole among those that have ever been described in literary sources. This amphibole is characterized by single-crystal and powder X-ray diffraction, IR spectroscopic and optical data. The role of high barium activity in the formation of sulfide-free ores of chalcophile elements has been substantiated. A possible mechanism of sulfur immobilization can be described by the scheme S2− + 2O2 ↔ SO42−; SO42− + Ba2+ → BaSO4↓.

Gasparite-(La), La(AsO4), is a new mineral (IMA 2018-079) from Mn ores of the Ushkatyn-III deposit, Central Kazakhstan (type locality) and from alpine fissures in metamorphic rocks of the Wanni glacier, Binn Valley, Switzerland (co-type locality). Gasparite-(La) is named for its dominant lanthanide, according to current nomenclature of rare-earth minerals. The occurrences and parageneses in both localities are distinct: minute isometric grains up to 15 μm in size, associated with friedelite, jacobsite, pennantite, manganhumite series minerals (alleghanyite, sonolite), sarkinite, tilasite, and retzian-(La) are typically embedded into calcite-rhodochrosite veinlets (Ushkatyn-III deposit) vs. elongated crystals up to 2 mm in size in classical alpine fissures in two-mica gneiss without indicative associated minerals (Wanni glacier). Their chemical compositions have been studied by EDX and WDX; crystal-chemical formulas of gasparite-(La) from the Ushkatyn-III deposit (holotype specimen) and Wanni glacier (co-type specimen) are (La0.65Ce0.17Nd0.07Ca0.06Mn0.05Pr0.02)1.02[(As0.70V0.28P0.02)1.00O4] and (La0.59Ce0.37Nd0.02 Ca0.02Th0.01)1.01[(As0.81P0.16Si0.02S0.02)1.01O4], respectively. In polished sections, crystals are yellow and translucent with bright submetallic luster. Selected reflectance values R1/R2 (λ, nm) for the holotype specimen in air are: 11.19/9.05 (400), 11.45/9.44 (500), 10.85/8.81 (600), 11.23/9.08 (700). The structural characteristics of gasparite-(La) were studied by means of EBSD (holotype specimen), XRD, and SREF (co-type specimen). Gasparite-(La) has a monoclinic structure with the space group P21/n. Our studies revealed that gasparite-(La) from the Ushkatyn-III deposit and Wanni glacier have different origins. La/Ce and As/P/V ratios in gasparite-(La) may be used as an indicator of formation conditions.

Pentacarbonyl complexes of 99Tc and Re [M(CAP)(CO)5]X and [M(PTA)(CO)5]X (M = 99Tc or Re and X = ClO4− or OTf–) with aminophosphine ligands 1,4,7-triaza-9-phosphatricyclo[5.3.214,9]tridecane (CAP) and 1,3,5-triaza-7-phosphaadamantane (PTA) were prepared for the first time by the reaction of [MX(CO)5] (M = 99Tc or Re, X = ClO4− or OTf–) with CAP and PTA in CH2Cl2 at room temperature. The reaction of [TcCl(CO)5] with CAP in refluxing CH2Cl2 yields the tricarbonyl complex [99TcCl(CAP)2(CO)3]. Treatment of [Re(H2O)3(CO)3]Cl with CAP in aqueous solution at 40–50 °C gives the rhenium analog [ReCl(CAP)2(CO)3]. Both penta- and tricarbonyl phosphine complexes were characterized by spectroscopic methods (IR, NMR, MS) and single crystal X-ray diffraction. The [M(PTA)(CO)5]X complexes are soluble in aqueous solutions, whereas their CAP analogs are not. The CAP complexes become water-soluble after acidification with dilute acids. As the pH of their aqueous solutions increases, they start to slowly degrade at pH 8 and completely decompose at pH 14. In acidic media, the pentacarbonyl complexes undergo stepwise protonation and are stable indefinitely.

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.

Samarskite-(Y), the mineral known for almost 180 years only in metamict (X-ray amorphous) state, was found as non-metamict crystals in sanidinites of the Laach Lake (Laacher See), Eifel volcanic region, Germany. The crystal structure has been solved for the first time and refined to R1 = 1.1% based on 838 observed [I > 2σ(I)] independent reflections. Samarskite-(Y) is monoclinic, P2/c, a 9.8020(8), b 5.6248(3), c 5.2073(4) A, β 93.406(4)°, V 286.59(4) A3, Z = 2. The empirical formula (calculated on 8 O apfu) is $$\left[ {\left( {{\text{Y}}_{0. 2 5} Ln_{0. 1 8} } \right)_{\varSigma 0. 4 3} {\text{Th}}_{0. 3 7} {\text{U}}_{0. 1 3}^{ 4+ } {\text{Ca}}_{0.0 3} } \right]_{\varSigma 0. 9 6} \left( {{\text{Fe}}_{0. 7 3}^{ 3+ } {\text{Mn}}_{0. 1 8}^{ 2+ } } \right)_{\varSigma 0. 9 1} \left( {{\text{Nb}}_{ 1. 8 5} {\text{Ti}}_{0.0 6} {\text{Zr}}_{0.0 6} {\text{Ta}}_{0.0 3} {\text{W}}_{0.0 2} } \right)_{\varSigma 2.0 2} {\text{O}}_{ 8}$$ . Samarskite-(Y) from the type locality, the Blyumovskaya Pit, Ilmeny Mountains, South Urals, Russia, was studied for comparison; electron microprobe data showed the same species-defining constituents and stoichiometry: $$\left[ {\left( {{\text{Y}}_{0. 3 4} Ln_{0. 20} } \right)_{\varSigma 0. 5 4} {\text{U}}_{0. 4 2}^{ 4+ } {\text{Th}}_{0.0 3} } \right]_{\varSigma 0. 9 9} \left( {{\text{Fe}}_{0. 8 6}^{ 3+ } {\text{Mn}}_{0.0 8}^{ 2+ } } \right)_{\varSigma 0. 9 4} \left( {{\text{Nb}}_{ 1. 1 4} {\text{Ta}}_{0. 70} {\text{Ti}}_{0. 1 5} } \right)_{\varSigma 1. 9 9} {\text{O}}_{ 8}$$ . Samarskite-(Y) is the first example of cation-ordered niobate structurally related to layered double tungstates AMW2O8, the compounds used as luminophors and active media in solid-state lasers. The pseudo-layered framework of the mineral can be derived from that of wolframite via substitution of W for Nb, whereas each second [FeO6] layer is replaced by [YO8] one. The resulting sequence of layers can be expressed as -[AO8]-[BO6]-[MO6]-[BO6]- leading to the formula AMB2O8 in which A = Y, Ln, Th, U4+, Ca; M = Fe3+, Mn2+; and B = Nb, Ta, Ti. The end-member formula of samarskte-(Y) is YFe3+Nb2O8 (approved by the Commission on New Minerals, Nomenclature and Classification, International Mineralogical Association, memorandum 90-FH/18).

The new mineral anatolyite Na6(Ca,Na)(Mg,Fe3+)3Al(AsO4)6 was found in the Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. It is associated with potassic feldspar, hematite, tenorite, cassiterite, johillerite, tilasite, ericlaxmanite, lammerite, arsmirandite, sylvite, halite, aphthitalite, langbeinite, anhydrite, wulffite, krasheninnikovite, fluoborite, pseudobrookite and fluorophlogopite. Anatolyite occurs as aggregates (up to 2 mm across) of rhombohedral–prismatic, equant or slightly elongated along [001] crystals up to 0.2 mm. The mineral is transparent, pale brownish–pinkish, with vitreous lustre. It is brittle, cleavage was not observed and the fracture is uneven. The Mohs’ hardness is ca 4½. Dcalc is 3.872 g cm–3. Anatolyite is optically uniaxial (–), ω = 1.703(4) and ε = 1.675(3). Chemical composition (wt.%, electron microprobe) is: Na2O 16.55, K2O 0.43, CaO 2.49, MgO 5.80, MnO 0.16, CuO 0.69, ZnO 0.55, Al2O3 5.01, Fe2O3 7.94, TiO2 0.18, SnO2 0.17, SiO2 0.04, P2O5 0.55, As2O5 60.75, SO3 0.03, total 101.34. The empirical formula based on 24 O apfu is (Na5.90K0.10)Σ6.00(Ca0.50Na0.13Zn0.08Mn0.03)Σ0.74(Mg1.63Fe3+1.12Al0.15Cu0.10)Σ3.00(Al0.96Ti0.03Sn0.01)Σ1.00(As5.97P0.09Si0.01)Σ6.07O24. Anatolyite is trigonal, R$\bar{3}$c, a = 13.6574(10), c = 18.2349(17) Å, V = 2945.6(4) Å3 and Z = 6. The strongest reflections of the powder XRD pattern [d,Å(I)(hkl)] are: 7.21(33)(012), 4.539(16)(113), 4.347(27)(211), 3.421(20)(220), 3.196(31)(214), 2.981(17)(223), 2.827(100)(125) and 2.589(18)(410). The crystal structure was solved from single-crystal XRD data to R = 4.77%. The structure is based on a 3D heteropolyhedral framework formed by M4O18 clusters [M1 = Al and M2 = (Mg,Fe3+)] linked with AsO4 tetrahedra. (Ca,Na) and Na cations centre A1O6 and A2O8 polyhedra in voids of the framework. Anatolyite is isostructural with yurmarinite. The new mineral is named in honour of the outstanding Russian crystallographer, mineralogist and mathematician Anatoly Kapitonovich Boldyrev (1883–1946).

The new mineral kruijenite, ideally Ca4Al4(SO4)F2(OH)16·2H2O, was found in a calcic xenolith from tephra of the Feuerberg paleovolcano situated near Daun, Eifel paleovolcanic region, Rhineland-Palatinate, Germany. It is associated with fluorite, calcite, aragonite, cuspidine, magnesioferrite, hematite, sharyginite, harmunite, and an insufficiently investigated hydrous Ca-Mg-Al silicate. Kruijenite occurs as pale greenish-yellow to colourless long prismatic tetragonal crystals up to 0.1 mm × 1 mm in cavities typically combined in radiating or random aggregates. The mineral is brittle, with Mohs’ hardness of 3; Dcalc is 2.573 g/cm3. The IR spectrum is given. Kruijenite is optically uniaxial (−), ω = 1.576(3), e = 1.561(3). The chemical composition (wavelength dispersive spectrometer Oxford INCA Wave 700 EPMA analyser, H2O calculated from structural data) is: CaO 32.38 wt%, Al2O3 27.75 wt%, Cr2O3 1.45 wt%, SO3 8.09 wt%, F 5.84 wt%, H2O 25.64 wt%, –O=F –2.46 wt%, total 98.69 wt%. The empirical formula is Ca4.00(Al3.77Cr0.13)Σ3.90(SO4)0.70F2.13(OH)16.17·1.79H2O (Z = 2). Kruijenite is tetragonal, space group P4/ncc, a = 12.9299(4) A, c = 5.2791(3) A, V = 882.57(6) A3, Z = 2. The crystal structure was solved and refined to R = 0.121. Kruijenite represents a novel structure type. Its structure is based on the microporous pseudo-framework built by Al(OH)6 octahedra and CaF2(OH)6 polyhedra. The strongest reflections of the powder X-ray diffraction pattern [d (I) (hkl)] are: 9.12 A (77%) (110), 4.565 A (100%) (220), 4.084 A (50%) (310), 2.964 A (74%) (321), 2.694 A (27%) (411), 2.321 A (24%) (431), 2.284 A (29%) (511), 2.217 A (22%) (321, 530), 1.971 A (40%) (611). The mineral is named in honor of the Dutch collector of Eifel minerals Fred Kruijen (born in 1956).

Belogubite, ideally CuZn(SO 4 ) 2 ·10H 2 O, has been found in the supergene zone uncovered by the open pit at the Gayskoe massive sulfide Zn-Cu deposit (Orenburgskaya region, the South Urals, Russia). It is associated with dietrichite and may contain relics of quartz. Belogubite forms aggregates of blue grains up to 1 mm in size. The mineral is transparent with vitreous luster and white streak. Its color varies from pale equant to light blue. Cleavage and parting were not observed. The new mineral is brittle and has Mohsʼ hardness ca . 2½. Its density measured by floatation in bromoform+ethanol is 2.27(2) g/cm –3 , its calculated density is 2.249 g/cm –3 . Belogubite is biaxial (–), α = 1.512(2), β = 1.525(2), γ = 1.531(2); 2 V (meas.) = 70(10)°, 2 V (calc.) = 67.9°. Dispersion is noticeable, r

Allabogdanite, (Fe,Ni)2P, is the only known natural high-pressure phase reported in the Fe–Ni–P system. The mineral, which was previously described from a single meteorite, the Onello iron, is now discovered in the Santa Catharina and Barbianello nickel-rich ataxites. The occurrence of allabogdanite in Santa Catharina, one of the largest and well-studied meteorites, suggests that this mineral is more common than was believed. The formation of allabogdanite-bearing phosphide assemblages in a given meteorite provides evidence that it experienced peak pressure of at least 8 GPa at a temperature above 800 °C. Since the pressure-temperature stability parameters of allabogdanite fall within the margins of the stishovite (rutile-type SiO2) stability area, the former can be employed as a convenient stishovite-grade indicator of significant impact events experienced by iron and stony-iron meteorites and their parent bodies.

Centimeter-sized crystals of orthorhombic calcium formate, α-Ca(HCO2)2 from Alkali Lake, Oregon, USA have been studied by means of powder and single-crystal X-ray diffraction analysis, infrared, and Raman spectroscopy. Based on the data on carbon isotope abundance in calcium formate and associated minerals, it was concluded that the formation of α-Ca(HCO2)2 may be a result of a combination of two factors: lake microbial metabolism and anthropogenic pollution with Agent Orange. Possible causes of stability of the low-density tetragonal β-Ca(HCO2)2 polymorph (formicaite) in boron ores are discussed.

The synthetic nosean- and hauyne-like aluminosilicates with (MoO4)2− and (WO4)2− extra-framework anions were synthesized in H2O-bearing systems (3 kbar, 750 °C) and studied by means of electron microprobe analysis, Raman spectroscopy, powder and single-crystal X-ray diffraction. The nosean-like phase contains up to 10.6 wt% MoO3 and up to 5.1 wt% WO3; the maximum content of MoO3 in the hauyne-like phase is 22.5 wt%. The nosean-like phase with (MoO4)2− and (WO4)2− is cubic, P-43m, a = 9.1278(10) A, V = 760.498(14) A3, Z = 1. This compound with the crystal chemical formula Na7.68[(Al,Si)12O24] {[(Mo0.65W0.35)O4]0.78□0.22}·H2O has a disordered Al/Si framework, that is caused by the high temperature of crystallization (t = 750 °C) with further quenching at room temperature. Despite the same conditions of synthesis, the hauyne-like phase with (MoO4)2−, Na5.12Ca1.92[Al6Si6O24](MoO4)1.52 has an Al/Si-ordered framework. Its space group is P-43n, a = 9.1516(4) A, V = 766.46(6) A3, Z = 1. In both synthesized sodalite-type aluminosilicates the anion groups (MoO4)2− and (WO4)2− are dynamically disordered. The polarized Raman spectra of both aluminosilicates show that Raman-active modes of (MoO4)2− and (WO4)2− correspond to vibrations of tetrahedral anions with symmetry Td. The presence of H2O was fixed only in the nosean-like compound and no preferred orientation of water molecule was detected.

The new crichtonite-group mineral saranovskite, ideally SrCaFe2+2(Cr4Ti2)Ti12O38, was discovered in the Glavnoe Saranovskoe deposit, Middle Urals, Russia, and named after the type locality. The associated minerals are chromite, Cr-bearing clinochlore, and calcite. Saranovskite forms black crude equant crystals about 2 mm across. The lustre is submetallic, and the streak is brownish-gray. Cleavage is not observed. The Mohs hardness is 6. Density calculated using the empirical formula is equal to 4.501 g cm–3. The reflectance spectra in visible range are given. The IR spectrum shows the absence of H-, B- and C-bearing groups. The Raman spectrum of saranovskite confirms the absence of H-bearing groups and indicates a rather high degree of ordering of Ti4+ and lower-valence cations. The chemical composition of saranovskite is (wt.%; electron microprobe, total iron apportioned between FeO and Fe2O3 taking into account charge balance): MgO 2.01, CaO 1.43, MnO 0.21, FeO 8.14, SrO 3.27, BaO 2.18, Al2O3 0.53, Sc2O3 0.69, Cr2O3 10.27, Fe2O3 2.19, Y2O3 1.56, La2O3 0.94, Ce2O3 0.91, Pr2O3 0.14, Nd2O3 0.35, TiO2 64.25, ZrO2 0.58, total 99.65. The crystal chemical formula of saranovskite is (Sr0.55Ba0.25Ln0.10Ca0.10)(Ca0.36Y0.25Ln0.16Fe2+0.08Zr0.10Mn0.05) (Fe2+1.12Mg0.88)(Cr3+2.34Ti2.28Fe2+0.91Fe3+0.11Al0.18Sc3+0.18)(Ti5.82Fe3+0.18)Ti6.0O38. The idealized formula is SrCaFe2+2(Cr4Ti2)Ti12O38. The crystal structure was determined using single-crystal X-ray diffraction data and refined to R = 0.0243. The new mineral is isostructural to other crichtonite-group members. Saranovskite is trigonal, space group R $$\overline{3}$$ , with a = 10.3553(2) A, c = 20.7301(4) A, V = 1925.12(8) A3 and Z = 3. The strongest lines of the powder X-ray diffraction pattern [d, A (I, %) (hkl)] are: 3.398 (75) (024), 2.881 (100) (– 126), 2.842 (65) (– 234), 2.247 (67) (– 144). 2.137 (76) (– 345), 1.799 (63) (– 348), 1.597 (72) (– 1.4.10, 152), 1.439 (76) (520).

Three new borate minerals rhabdoborite-(V), rhabdoborite-(Mo) and rhabdoborite-(W), forming the rhabdoborite group, are found in the Arsenatnaya fumarole, Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. They are closely associated with each other and anhydrite, diopside, hematite, schaferite, berzeliite, svabite, calciojohillerite, ludwigite, forsterite, magnesioferrite, baryte, fluorapatite, udinaite, arsenudinaite, and powellite. Rhabdoborites form long-prismatic to acicular crystals up to 0.04 × 0.04 × 7 mm3 typically combined in aggregates up to 1 cm. They are transparent, light yellow, with vitreous lustre. The empirical formulae of holotypes, calculated based on 26 O + F apfu, are: rhabdoborite-(V): (Mg11.85Fe3+0.11Mn0.06Ca0.02)Σ12.04(V5+0.70Mo6+0.36W6+0.21Te6+0.01)Σ1.28[(P0.35As5+0.16)Σ0.51B5.50]Σ6.01O24.35F1.65; rhabdoborite-(Mo): (Mg11.78Mn0.07Fe3+0.06Ca0.06)Σ11.97(Mo6+0.65V5+0.49W6+0.19)Σ1.33[(P0.31As5+0.14)Σ0.45B5.54]Σ5.99O24.33F1.67; rhabdoborite-(W): (Mg11.74Fe3+0.09Ca0.03Mn0.02)Σ11.88(W6+0.75V5+0.44Mo6+0.13)Σ1.32[(P0.25As5+0.13)Σ0.38B5.65]Σ6.03O24.42F1.58. The simplified formulae are: rhabdoborite-(V): $${{\text{Mg}}_{12}}({\text{V}}^{5+}, M^{6+})_{1\nicefrac{1}{3}}{{\text{O}}_{6}}$$ {(BO3)6–x(PO4)xF2–x} (M6+ = Mo, W and x

A new alluaudite-group mineral zincobradaczekite, a Zn–Cu ordered highly zincian analogue of bradaczekite, was discovered in sublimates of the Yadovitaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with bradaczekite, lammerite, lammerite-β, borisenkoite, mcbirneyite, sanidine, hematite, tenorite, pseudolyonsite, lyonsite, starovaite, rutile, tripuhyite, pseudobrookite, piypite, langbeinite, calciolangbeinite, aphthitalite, alumoklyuchevskite, and palmierite. Zincobradaczekite forms oblique-angled prismatic crystals up to 0.02 × 0.02 × 0.08 mm3 and equant or tabular crystals up to 0.05 mm. It is transparent, blue, greenish-blue, grey-blue or bluish-grey. The lustre is vitreous. Dcalc is 4.71 g cm−3. Zincobradaczekite is optically biaxial (–), α 1.786(5), β 1.846(8), γ 1.90(1), 2Vmeas. 80(5)o. Chemical composition (wt%, electron microprobe) is Na2O 4.07, K2O 0.53, CaO 0.01, MgO 0.71, MnO 0.01, CuO 19.89, ZnO 24.21, Al2O3 0.02, Fe2O3 0.90, TiO2 0.03, P2O5 0.41, V2O5 1.05, As2O5 47.10, SO3 1.01, and total 99.95. The empirical formula based on 12 O apfu is Na0.90K0.08Cu1.70Mg0.12Zn2.03Fe3+0.08(As2.79S0.09V0.08P0.04)Σ3.00O12. The simplified chemical formula is NaCu2Zn2(AsO4)3. Zincobradaczekite is monoclinic, C2/c, a 12.0375(13), b 12.4500(13), c 7.2213(8) A, β 117.506(7)o, V 959.90(18) A3 and Z 4. The strongest reflections of the powder XRD pattern [d,A(I)(hkl)] are 6.21(31)(020), 3.416(70)(310, − 112), 3.200(17)(002), 2.779(23)(− 402), 2.691(100)(− 132, 240), 1.841(20)(152) and 1.680(14)(− 642). The crystal structure was solved (single-crystal XRD, R = 4.38%). The simplified crystal chemical formula is A(1)□A(1)ʹCuA(2)□A(2)ʹNaM(1)CuM(2)Zn2(AsO4)3 (□—vacancy) and the end-member formula is NaCuCuZn2(AsO4)3. Zincobradaczekite and bradaczekite, ideally NaCuCuCu2(AsO4)3, are isostructural. In the Yadovitaya fumarole, Mg-poor bradaczekite forms an isomorphous series with zincobradaczekite, whilst in the neighbouring Arsenatnaya fumarole only a Zn-depleted and Mg-enriched variety of bradaczekite occurs. Zincobradaczekite and bradaczekite differ from other anhydrous alluaudite-group arsenates by increased values of the c and β unit-cell parameters due to the strong Jahn–Teller distortion of M(1)O6 octahedron predominantly occupied with Cu2+.

A new pumpellyite-group mineral shuiskite-(Cr), ideally Ca2CrCr2[SiO4][Si2O6(OH)](OH)2O, was found at the Rudnaya mine, Glavnoe Saranovskoe deposit, Middle Urals, Russia. It occurs on the walls of 0.5 to 1 cm thick fractures in chromitite, filled with calcite, Cr-bearing clinochlore, and uvarovite. Shuiskite-(Cr) forms long prismatic to acicular crystals up to 0.1 &times, 0.5 &times, 7 mm elongated along [010] and slightly flattened on [100]. The crystals are commonly combined into radial, sheaf-like aggregates. Most observed crystals are simple twins with a (001) composition plane. Shuiskite-(Cr) is greenish-black under daylight or purplish-black under incandescent light. It is optically biaxial (&ndash, ), &alpha, = 1.757(5), &beta, = 1.788(6), &gamma, = 1.794(6), 2V (meas.) = 45(10)&deg, 2V (calc.) = 46&deg, (589 nm). The Dcalc is 3.432 g/cm3. The IR spectrum is reported. The chemical composition (wt.%) is CaO 21.33, MgO 3.17, Al2O3 5.41, Cr2O3 28.50, TiO2 0.18, SiO2 33.86, H2O 5.82, total 98.27. The empirical formula calculated based on the sum of eight metal cations and Si atoms per formula unit is Ca2.02Mg0.42Cr3+1.99Al0.56Ti0.01Si3.00O10.57(OH)3.43. The simplified formula is Ca2(Cr,Mg)(Cr,Al)2[SiO4][Si2O6(OH,O)](OH,O)(OH)2. Shuiskite-(Cr) is monoclinic, C2/m, a = 19.2436(6), b = 5.9999(2), c = 8.8316(3) &Aring, &beta, = 97.833(3)&deg, V = 1010.17(6) &Aring, 3, and Z = 4. The crystal structure, solved from single-crystal X-ray diffraction data (R = 0.0469), is based on a pair of chains of edge-sharing Cr-centred octahedra running along the b axis, linked together via the [SiO4] and [Si2O6(OH)] groups and Ca-centred polyhedra. The mineral species shuiskite, ideally Ca2MgCr2[SiO4][Si2O6(OH)](OH)3, was renamed to shuiskite-(Mg) by the decision of the IMA CNMNC. The shuiskite solid solution series with the general formula Ca2XCr2[SiO4][Si2O6(OH,O)](OH)2(OH,O), which includes shuiskite-(Mg) and shuiskite-(Cr) with X = Mg and Cr3+, respectively, appeared in the pumpellyite group.

The chemistry of noble gases was for a long time dominated by fluoride-bearing compounds of xenon. However, the last two decades have brought new insights into the chemistry of xenon oxides and oxysalts, including insights involving a novel type of non-covalent interaction (aerogen bonding), discoveries of new xenon oxides, oxide perovskite frameworks and evidence for an abrupt increase of xenon reactivity under extreme pressure-temperature conditions. The complex implementation of these findings could facilitate the development of explanations for long-standing interdisciplinary problems, such as the depletion of heavy noble gases in contemporary planetary atmospheres – the cosmochemical enigma known as the “missing xenon” paradox.

A new mineral, krasnoshteinite (Al8[B2O4(OH)2](OH)16Cl4&sdot, 7H2O), was found in the Verkhnekamskoe potassium salt deposit, Perm Krai, Western Urals, Russia. It occurs as transparent colourless tabular to lamellar crystals embedded up to 0.06 x 0.25 x 0.3 mm in halite-carnallite rock and is associated with dritsite, dolomite, magnesite, quartz, baryte, kaolinite, potassic feldspar, congolite, members of the goyazite&ndash, woodhouseite series, fluorite, hematite, and anatase. Dmeas = 2.11 (1) and Dcalc = 2.115 g/cm3. Krasnoshteinite is optically biaxial (+), &alpha, = 1.563 (2), &beta, = 1.565 (2), &gamma, = 1.574 (2), and 2Vmeas = 50 (10)&deg, The chemical composition (wt.%, by combination of electron microprobe and ICP-MS, H2O calculated from structure data) is: B2O3 8.15, Al2O3 46.27, SiO2 0.06, Cl 15.48, H2Ocalc. 33.74, &ndash, O=Cl &ndash, 3.50, totalling 100.20. The empirical formula calculated based on O + Cl = 33 apfu is (Al7.87Si0.01)&Sigma, 7.88[B2.03O4(OH)2][(OH)15.74(H2O)0.26]&Sigma, 16[(Cl3.79(OH)0.21]&Sigma, 4&sdot, 7H2O. The mineral is monoclinic, P21, a = 8.73980 (19), b = 14.4129 (3), c = 11.3060 (3) &Aring, &beta, = 106.665 (2)&deg, V = 1364.35 (5) &Aring, 3, and Z = 2. The crystal structure of krasnoshteinite (solved using single-crystal data, R1 = 0.0557) is unique. It is based upon corrugated layers of Al-centered octahedra connected via common vertices. BO3 triangles and BO2(OH)2 tetrahedra share a common vertex, forming insular [B2O4(OH)2]4&minus, groups (this is a novel borate polyanion) which are connected with Al-centered octahedra via common vertices to form the aluminoborate pseudo-framework. The structure is microporous, zeolite-like, with a three-dimensional system of wide channels containing Cl- anions and weakly bonded H2O molecules. The mineral is named in honour of the Russian mining engineer and scientist Arkadiy Evgenievich Krasnoshtein (1937&ndash, 2009). The differences in crystal chemistry and properties between high-temperature and low-temperature natural Al borates are discussed.

Halamishite, Ni5P4, is a new natural phosphide discovered in pyrometamorphic assemblages of the Hatrurim Formation (Mottled Zone), Southern Levant. The mineral occurs as minute grains up to 20 μm in size intimately intergrown with zuktamrurite, FeP2, and transjordanite, (Ni,Fe)2P, which are disseminated in fine-grained diopside microbreccia. Chemical composition of the holotype material (electron microprobe, wt%): Ni 69.23, Fe 1.80, P 29.59, total 100.62, was recalculated to (Ni4.90Fe0.13)5.03P3.97 on the basis of nine atoms per formula unit. The ideal formula of halamishite is Ni5P4. In reflected light, the mineral is white with beige tint, non-pleochroic. It is moderately anisotropic and bireflectant (ΔR589 = 7.2%). Reflectance values for the four wavelengths recommended by the IMA Commission on Ore Microscopy are [Rmax/Rmin (%), λ (nm)]: 44.3/36.6, 470; 49.2/42.1, 546; 51.3/44.1, 589; 53.3/46.1, 650. Crystal structure of halamishite was solved and refined to R1 = 0.031 based on 425 unique observed [I ≥ 2σ(I)] reflections. The mineral is hexagonal, space group P63mc, a 6.8184(4), c 11.0288(8) A, V 444.04(6) A3, Z = 4. Dx calculated for an empirical formula is 6.249(1) g cm−3. Halamishite is named for its type locality, the Halamish wadi in the Hatrurim basin, Negev Desert, Israel. It is a naturally occurring analogue of synthetic Ni5P4, the compound widely used in electro- and photocatalytic applications. Due to chemical proximity to the Ni5P4 end-member, halamishite can be used as a geothermometer indicating that formation of phosphide assemblages had occurred at a temperature below 870 °C.

Murashkoite, FeP, is a new mineral found in pyrometamorphic rocks of the Hatrurim Formation, South Levant. It is a typical accessory phase in the marbles and paralavas in the southern Negev Desert, Israel and on the Transjordan Plateau, Jordan. Murashkoite occurs as grains and aggregates up to 2 mm closely associated with barringerite, (Fe,Ni)2P, and zuktamrurite, FeP2. The rock-forming minerals include pyroxenes of the diopside-hedenbergite series, anorthite with subordinate gehlenite, tridymite, cristobalite, pyrrhotite, fluorapatite, chromite, magnetite, hematite, merrillite and late hydrothermal carbonates, silicates and sulfates. Macroscopically, murashkoite is yellowish-grey in colour and has a metallic lustre. In reflected light, the mineral is white with a beige tint and it is non-pleochroic. The anisotropy is distinct, from yellow-grey to greyish-blue. Selected reflectance values [Rmax–Rmin, % (λ, nm)] are: 42.7–40.8 (400), 42.0–40.6 (500), 44.5–43.4 (600), 48.0–47.7 (700). It is brittle. VHN20 = 468 kg mm−2. The holotype material has the chemical composition (electron microprobe): Fe 63.82; Ni 0.88; P 35.56; total 100.26 wt.%. The empirical formula calculated on the basis of 2 apfu is (Fe0.99Ni0.01)1.00P1.00 corresponding to FeP. Murashkoite is orthorhombic, space group Pnma, unit cell parameters refined from the single-crystal data are: a 5.099(2), b 3.251(2), c 5.695(2) A, V 94.41(8) A3, Z = 4, Dx = 6.108(5) g cm−3. The crystal structure was solved and refined to R1 = 0.0305 on the basis of 131 unique reflections with I > 2σ(I). The strongest lines of the powder X-ray diffraction pattern [(d, A) (I, %) (hkl)]: 2.831(75)(002,011); 2.548(22)(200); 2.477(46)(102,111); 1.975(47)(112); 1.895(100)(202,211); 1.779(19)(103); 1.632(45)(013,301,020). The mineral is named in honour of Dr. Mikhail Nikolaevich Murashko (born 1952), for his contributions to the mineralogy of the Hatrurim Formation. Murashkoite is a natural counterpart of synthetic FeP, the compound widely used in heterogeneous catalysis and electrocatalysis.

Zuktamrurite, FeP2, is a new mineral, a natural iron diphosphide found in the pyrometamorphic rocks of the Hatrurim Formation, in the southern part of the Negev Desert, Israel and on the Transjordan Plateau, Jordan. The mineral occurs as irregular grains up to 50 µm in size associated with murashkoite, FeP, and barringerite, (Fe,Ni)2P. In reflected light, zuktamrurite is white with a distinct bluish tint. It is non-pleochroic but exhibits distinct anisotropy in bluish colours. Reflectance values for the IMA COM recommended wavelengths are [Rmax/Rmin, % (λ, nm)]: 50.40/47.20 (470); 49.16/46.23 (546); 48.97/46.16 (589); 49.40/46.40 (650). It is brittle. Electron microprobe analysis of the holotype specimen gave the following chemical composition (wt%, average of 5 points): Fe 40.23; Ni 7.97; P 51.70; total 99.90. The empirical formula calculated on the basis of 3 apfu is (Fe0.86Ni0.16)1.02P1.98 corresponding to FeP2. Zuktamrurite is orthorhombic, space group Pnnm, unit cell parameters refined from the single-crystal data: a 4.9276(6), b 5.6460(7), c 2.8174(4) A, V 78.38(1) A3, Z = 2. Dx = 5.003 g cm−3. The crystal structure was solved and refined to R1 = 0.0121 on the basis of 109 unique reflections with I > 2σ(I). The strongest lines of the powder X-ray diffraction pattern [(d, A) (I, %) (hkl)]: 3.714 (54) (110); 2.820 (31) (020); 2.451 (100) (120, 101); 2.242 (55) (111); 1.760 (37) (211). The mineral is named for the Zuk-Tamrur cliff (Dead Sea) located nearby the type locality, the Halamish Wadi, southern Negev Desert, Israel. Zuktamrurite is the phosphide analogue of lollingite (loellingite), FeAs2. It is the most phosphorus-rich phosphide ever found in nature.

The influence of pentavalent arsenic and phosphorus on crystal chemical features of the feldspar framework was studied on the minerals belonging to the sanidine–filatovite solid-solution series from fumarolic exhalations of the Tolbachik volcano (Kamchatka, Russia). The reported feldspars demonstrate the first example of natural continuous solid solution between silicate and arsenate. The content of As2O5 varies from 0.0 to 45 wt% along with the highest phosphorus content found in natural feldspars: up to 5 wt% P2O5. The major substitution schemes in the studied feldspars are Al3+ + M5+ → 2Si4+ and M2+ + M5+ → Al3+ + Si4+, where M2+ = Zn and Cu and M5+ = As and P. The crystal structures of four samples with empirical formulae K0.95[(Si2.98Al0.93Fe0.08As0.02)Ʃ4.01O8] (space group C2/m), (K0.91Na0.06Ca0.03)Ʃ1.00[(Si2.81Al1.14As0.03P0.03Fe0.01)Ʃ4.02O8] (C2/m), K0.82[(Al1.92As1.11Si0.89Zn0.05Fe0.03Cu0.02P0.01)Ʃ4.03O8] (I2/c), K0.99[(Si1.87Al1.51As0.53P0.05Fe0.02Cu0.01)Ʃ3.99O8] (I2/c) were studied. The phase transition in the sanidine–filatovite solid-solution series is C2/m → I2/c. This is caused by the change of the Al:(Si + As) ratio from 1:3 in sanidine to 1:1 in filatovite along with significant ordering of Al, Si and As in the framework.

An alteration of the uranyl oxide hydroxy-hydrate mineral schoepite [(UO2)8O2(OH)12](H2O)12 at mild hydrothermal conditions was studied. As the result, four different crystalline phases Cs[(UO2)(SO4)(OH)](H2O)0.25 (1), Cs3[(UO2)4(SO4)2O3(OH)](H2O)3 (2), Cs6[(UO2)2(SO4)5](H2O)3 (3), and Cs2[(UO2)(SO4)2] (4) were obtained, including three novel compounds. The obtained Cs uranyl sulfate compounds 1, 3, and 4 were analyzed using single-crystal XRD, EDX, as well as topological analysis and information-based structural complexity measures. The crystal structure of 3 was based on the 1D complex, the topology of which was unprecedented for the structural chemistry of inorganic oxysalts. Crystal chemical analysis performed herein suggested that the majority of the uranyl sulfates minerals were grown from heated solutions, and the temperature range could be assumed from the manner of interpolyhedral linkage. The presence of edge-sharing uranyl bipyramids most likely pointed to the temperatures of higher than 100 &deg, C. The linkage of sulfate tetrahedra with uranyl polyhedra through the common edges involved elevated temperatures but of lower values (~70&ndash, 100 &deg, C). Complexity parameters of the synthetic compounds were generally lower than that of uranyl sulfate minerals, whose structures were based on the complexes with the same or genetically similar topologies. The topological complexity of the uranyl sulfate structural units contributed the major portion to the overall complexity of the synthesized compounds, while the complexity of the respective minerals was largely governed by the interstitial structure and H-bonding system.

The new mineral triazolite is found in a guano deposit located on the Pabellón de Pica Mountain, Iquique Province, Tarapacá Region, Chile. Associated minerals are salammoniac, halite, dittmarite, joanneumite, chanabayaite, nitratine, natroxalate and möhnite. Triazolite occurs as deep blue prismatic crystals up to 0.1 mm × 0.15 mm × 0.75 mm and their radial aggregates up to 1.5 mm across. The mineral is brittle. Its Mohs hardness is 2.Dcalc= 2.028 g cm–3. The infrared spectrum shows the presence of 1,2,4-triazolate anion and ammonia and water molecules. Triazolite is optically biaxial (–), α = 1.582(4), β = 1.625(3), γ = 1.625(3) and 2Vmeas= 5(3)°. The chemical composition (electron-microprobe data for Cl, Na, Fe and Cu; H, C, N and S contents were measured by gas chromatography of products of ignition at 1200°C; wt.%) is: Na 4.91, Fe 1.51, Cu 22.06, Cl 19.80, S 1.4, C 7.7, H 4.4, N 24.2, O (calc.) 12.83, total 98.81. The empirical formula is Na1.14(Cu1.86Fe0.14)(Cl2.99S0.23)N9.23C3.43H23.34O4.29. The idealized formula is NaCu2(N3C2H2)2(NH3)2Cl3·4H2O. Triazolite is a metalorganic ammine complex in which 1,2,4-triazolate anion and ammonia molecule are ligands coordinating Cu2+. The crystal structure was solved by direct methods and refined toR= 0.0242 based on 4210 unique reflections withI> 2σ(I). Triazolite is orthorhombic, space groupP212121,a= 19.3575(5),b= 7.15718(19),c= 12.5020(4) Å,V= 1732.09(8) Å3andZ= 4. The eight strongest reflections of the powder X-ray diffraction pattern [d, Å (I,%) (hkl)] are: 10.22 (97) (101), 6.135 (40) (011), 5.696 (17) (301), 5.182 (59) (202), 5.119 (100) (211), 4.854 (19) (400), 3.752 (16) (312, 501), 3.294 (18) (221). Triazolite is named for the presence of 1,2,4-triazolate anion.

The new eudialyte-group mineral siudaite, ideally Na8(Mn2+2Na)Ca6Fe3+3Zr3NbSi25O74(OH)2Cl·5H2O, was discovered in a peralkaline pegmatite situated at the Eveslogchorr Mt., Khibiny alkaline massif, Kola Peninsula, Russia. The associated minerals are aegirine, albite, microcline, nepheline, astrophyllite, and loparite-(Ce). Siudaite forms yellow to brownish-yellow equant anhedral grains up to 1.5 cm across. Its lustre is vitreous, and the streak is white. Cleavage is none observed. The Mohs’ hardness is 4½. Density measured by hydrostatic weighing is 2.96(1) g/cm3. Density calculated using the empirical formula is equal to 2.973 g/cm3. Siudaite is nonpleochroic, optically uniaxial, negative, with ω = 1.635(1) and e = 1.626(1) (λ = 589 nm). The IR spectrum is given. The chemical composition of siudaite is (wt%; electron microprobe, H2O determined by HCN analysis): Na2O 8.40, K2O 0.62, CaO 9.81, La2O3 1.03, Ce2O3 1.62, Pr2O3 0.21, Nd2O3 0.29, MnO 6.45, Fe2O3 4.51. TiO2 0.54, ZrO2 11.67, HfO2 0.29, Nb2O5 2.76, SiO2 47.20, Cl 0.54, H2O 3.5, –O = Cl − 0.12, total 99.32. According to Mossbauer spectroscopy data, all iron is trivalent. The empirical formula (based on 24.5 Si atoms pfu, in accordance with structural data) is [Na7.57(H2O)1.43]Σ9(Mn1.11Na0.88Ce0.31La0.20Nd0.05Pr0.04K0.41)Σ3(H2O)1.8(Ca5.46Mn0.54)Σ6(Fe3+1.76Mn2+1.19)Σ2.95Nb0.65(Ti0.20Si0.50)Σ0.71(Zr2.95Hf0.04Ti0.01)Σ3Si24.00Cl0.47O70(OH)2Cl0.47·1.82H2O. The crystal structure was determined using single-crystal X-ray diffraction data. The new mineral is trigonal, space group R3m, with a = 14.1885(26) A, c = 29.831(7) A, V = 5200.8(23) A3 and Z = 3. Siudaite is chemically related to georgbarsanovite and is its analogue with Fe3+-dominant M2 site. The strongest lines of the powder X-ray diffraction pattern [d, A (I, %) (hkl)] are: 6.38 (60) (–114), 4.29 (55) (–225), 3.389 (47) (131), 3.191 (63) (–228). 2.963 (100) (4–15), 2.843 (99) (–444), 2.577 (49) (3–39). Siudaite is named after the Polish mineralogist and geochemist Rafal Siuda (b. 1975).

Three novel uranyl selenate and sulfate oxysalts templated by protonated azetidine molecules, [ Az H] + , and its ring-opened counterpart 1-azetidinepropanamine, [ Az H(CH 2 ) 3 NH 3 ] 2+ , have been prepared and studied by X-ray structural analysis. Conformations of azetidinium cations were analysed by means of infrared vibrational assignments supported by the DFT calculations. Crystallization of [ Az H] 2 [(UO 2 ) 2 (SeO 4 ) 3 (H 2 O)] ( I ) from highly acidic solutions suggests that low pH does not necessarily result in the opening of azetidine ring. [ Az H(CH 2 ) 3 NH 3 ][(UO 2 ) 2 (SeO 4 ) 3 (H 2 O)](H 2 O) ( II ) and [ Az H(CH 2 ) 3 NH 3 ](H 5 O 2 )[(UO 2 ) 2 (SO 4 ) 3 (HSO 4 )] ( III ) are the first structurally characterized crystalline compounds bearing isolated ring-opened azetidine moiety.

The new zeolite martinandresite, ideally Ba2(Al4Si12O32)·10H2O, was discovered in the armenite locality of Wasenalp near the Isenwegg peak, Ganter valley, Simplon region, Switzerland. The associated minerals are armenite, quartz, dickite, and chlorite. Martinandresite forms tan-coloured blocky crystals up to 8 × 5 × 3.5 mm, their aggregates up to 6 cm across, as well as cruciform twins up to 3.5 mm. The major form is {010}; the subordinate forms are {100} and {001}. Indistinct cleavage is observed, presumably on (010) and in a direction across (010). The Mohs’ hardness is 4½. Density measured by flotation in heavy liquids is 2.482(5) g/cm3. Density calculated using the empirical formula is equal to 2.495 g/cm3. Martinandresite is optically biaxial, negative, α = 1.500(2), β = 1.512(2), γ = 1.515(2) (λ = 589 nm). 2V (meas.) = 55(10)°. The IR spectrum is given. The chemical composition of martinandresite is (wt%; electron microprobe, H2O determined by the modified Penfield method): Na2O 0.37, K2O 0.12, BaO 21.55, Al2O3 15.03, SiO2 49.86, H2O 12.57, total 99.50. The empirical formula based on 16 atoms Si + Al pfu is Na0.17K0.04Ba2.00(Al4.19Si11.81O32)H19.85O9.93. The crystal structure was determined using single-crystal X-ray diffraction data. The new mineral is orthorhombic, space group Pmmn, with a = 9.4640(5), b = 14.2288(6), c = 6.9940(4) A, V = 941.82(8) A3 and Z = 1. The crystal structure of martinandresite is unique and is based on the Al–Si–O tetrahedral framework containing four-, six- and eight-membered rings of tetrahedra. Si and Al are disordered between the two independent tetrahedral sites. The strongest lines of the powder X-ray diffraction pattern [d, A (I, %) (hkl)] are: 6.98 (74) (001), 6.26 (83) (011), 5.61 (100) (101), 3.933 (60) (220, 031), 3.191 (50) (112), 3.170 (62) (041), 3.005 (79) (231, 141). Martinandresite is named after Martin Andres (b. 1965), the discoverer of the armenite locality of Wasenalp.