The natural hydroniumjarosite sample from Cerros Pintados (Chile) was investigated by electron microprobe, single-crystal X-ray diffraction and vibrational spectroscopy (Infrared and Raman). The chemical composition of studied specimens (wt.%, mean of seven analyses) obtained from electron microprobe (in wt.%): Na2O 1.30, K2O 0.23, CaO 0.04, Fe2O350.49, Al2O30.37, SiO20.33, SO333.88, H2O (calculated on the basis of Σ(OH–+H3O+) deduced from the charge balance) 13.32, total 99.98, corresponds to the empirical formula (H3O)0.77+(Na0.20K0.02)∑0.22(Fe2.95Al0.03)∑2.98(OH)6.12[(SO4)1.97(SiO4)0.03]∑2.00(calculated on the basis of S + Si = 2 a.p.f.u. (atoms per formula unit)). The studied hydroniumjarosite is trigonal, with space groupRm, witha= 7.3408(2),c= 17.0451(6) Å andV= 795.46(4) Å3. The refined structure architecture is consistent with known jarosite-series minerals, including synthetic hydroniumjarosite. However, in the current study the presence of H3O+is well documented in difference Fourier maps, where characteristic positive difference Fourier maxima, with apparent trigonal symmetry, were localized in the vicinity of the O4 atom in the channel-voids of the structure. The structure of natural hydroniumjarosite, including the H atoms, was refined toR1= 0.0166 for 2113 unique observed reflections, withIobs>3σ(I). The present structure model, which includes the position of the H atom within the hydronium ion, is discussed with regard to the vibration spectroscopy results and earlier published density-functional theory (DFT) calculations for the alunite-like structure containing H3O+.

Two new minerals – manganoblödite (IMA2012–029), ideally Na2Mn(SO4)2·4H2O, and cobaltoblödite (IMA2012–059), ideally Na2Co(SO4)2·4H2O, the Mn-dominant and Co-dominant analogues of blödite, respectively, were found at the Blue Lizard mine, San Juan County, Utah, USA. They are closely associated with blödite (Mn-Co-Ni-bearing), chalcanthite, gypsum, sideronatrite, johannite, quartz and feldspar. Both new minerals occur as aggregates of anhedral grains up to 60 μm (manganoblödite) and 200 μm (cobaltoblödite) forming thin crusts covering areas up to 2 × 2 cm on the surface of other sulfates. Both new species often occur as intimate intergrowths with each other and also with Mn-Co-Ni-bearing blödite. Manganoblödite and cobaltoblödite are transparent, colourless in single grains and reddish-pink in aggregates and crusts, with a white streak and vitreous lustre. Their Mohs' hardness is ∼2½. They are brittle, have uneven fracture and no obvious parting or cleavage. The measured and calculated densities are Dmeas = 2.25(2) g cm−3 and Dcalc = 2.338 g cm−3 for manganoblödite and Dmeas = 2.29(2) g cm−3 and Dcalc = 2.347 g cm−3 for cobaltoblödite. Optically both species are biaxial negative. The mean refractive indices are α = 1.493(2), β = 1.498(2) and γ = 1.501(2) for manganoblödite and α = 1.498(2), β = 1.503(2) and γ = 1.505(2) for cobaltoblödite. The chemical composition of manganoblödite (wt.%, electron-microprobe data) is: Na2O 16.94, MgO 3.29, MnO 8.80, CoO 2.96, NiO 1.34, SO3 45.39, H2O (calc.) 20.14, total 98.86. The empirical formula, calculated on the basis of 12 O a.p.f.u., is: Na1.96(Mn0.44Mg0.29Co0.14Ni0.06)Σ0.93S2.03O8·4H2O. The chemical composition of cobaltoblödite (wt.%, electron-microprobe data) is: Na2O 17.00, MgO 3.42, MnO 3.38, CoO 7.52, NiO 2.53, SO3 45.41, H2O (calc.) 20.20, total 99.46. The empirical formula, calculated on the basis of 12 O a.p.f.u., is: Na1.96(Co0.36Mg0.30Mn0.17Ni0.12)Σ 0.95S2.02O8·4H2O. Both minerals are monoclinic, space group P21/a, with a = 11.137(2), b = 8.279(1), c = 5.5381(9) Å, β = 100.42(1)°, V = 502.20(14) Å3 and Z = 2 (manganoblödite); and a = 11.147(1), b = 8.268(1), C = 5.5396(7) Å, β = 100.517(11)°, V = 501.97(10) Å3 and Z = 2 (cobaltoblödite). The strongest diffractions from X-ray powder pattern [listed as (d,Å(I)(hkl)] are for manganoblödite: 4.556(70)(210, 011); 4.266(45)(01); 3.791(26)(11); 3.338(21)(310); 3.291(100)(220, 021), 3.256(67)(211, 21), 2.968(22)(21), 2.647(24)(01); for cobaltoblödite: 4.551(80)(210, 011); 4.269(50)(01); 3.795(18)(11); 3.339(43)(310); 3.29(100)(220, 021), 3.258(58)(11, 21), 2.644(21)(01), 2.296(22)(122). The crystal structures of both minerals were refined by single-crystal X-ray diffraction to R1 = 0.0459 (manganoblödite) and R1 = 0.0339 (cobaltoblödite).

Nestolaite (IMA 2013-074), CaSeO3·H2O, is a new mineral species from the Little Eva mine, Grand County, Utah, USA. It is named in honour of the prominent Italian mineralogist and crystallographer Fabrizio Nestola. The new mineral was found on sandstone matrix as rounded aggregates up to 2 mm across and up to 0.05 μm thick consisting of tightly intergrown oblique-angled, flattened to acicular crystals up to 30 μm long and up to 7 μm (very rarely up to 15 μm) thick. Nestolaite associates with cobaltomenite, gypsum, metarossite, orschallite and rossite. The new mineral is light violet and transparent with a white streak and vitreous lustre. The Mohs hardness is 2½. Nestolaite is brittle, has uneven fracture and perfect cleavage on {100}. The measured and calculated densities are Dmeas. = 3.18(2) g/cm3 and Dcalc. = 3.163 g/cm3. Optically, nestolaite is biaxial positive. The refractive indices are α = 1.642(3), β = 1.656(3), γ = 1.722(6). The measured 2V is 55(5)° and the calculated 2V is 51°. In transmitted light nestolaite is colourless. It does not show pleochroism but has strong pseudoabsorption caused by high birefringence. The chemical composition of nestolaite (wt.%, electronmicroprobe data) is: CaO 28.97, SeO2 61.14, H2O (calc.) 9.75, total 99.86. The empirical formula calculated on the basis of 4 O a.p.f.u. (atoms per formula unit) is Ca0.96Se1.02O3·H2O. The Raman spectrum is dominated by the Se–O stretching and O–Se–O bending vibrations of the pyramidal SeO3 groups and O–H stretching modes of the H2O molecules. The mineral is monoclinic, space group P21/c, with a = 7.6502(9), b = 6.7473(10), c = 7.9358(13) Å, β = 108.542 (12)°, V = 388.37(10) Å3 and Z = 4. The eight strongest powder X-ray diffraction lines are [dobs in Å(hkl) (Irel)]: 7.277 (100)(100), 4.949 (110)(37), 3.767 (002)(29), 3.630 (200)(58), 3.371 (020)(24), 3.163 (02)(74), 2.9783 (21)(74) and 2.7231 (112)(31). The crystal structure of nestolaite was determined by means of the Rietveld refinement from the powder data to Rwp = 0.019. Nestolaite possesses a layered structure consisting of CaΦ–SeO3 sheets, composed of edge-sharing polyhedra. Adjacent sheets are held by H bonds emanating from the single (H2O) group within the sheets. The nestolaite structure is topologically unique.

Calciodelrioite, ideally Ca(VO3)2(H2O)4, is a new mineral (IMA 2012-031) from the uraniumvanadium deposits of the eastern Colorado Plateau in the USA. The type locality is the West Sunday mine, Slick Rock district, San Miguel County, Colorado. The new mineral occurs on fracture surfaces in corvusite- and montroseite-impregnated sandstone and forms as a result of the oxidative alteration of these phases. At the West Sunday mine, calciodelrioite is associated with celestine, gypsum, huemulite, metarossite, pascoite and rossite. The mineral occurs as transparent colourless needles, bundles of tan to brown needles and star bursts of nearly black broad blades composed of tightly intergrown needles. Crystals are elongate and striated parallel to [100], exhibiting the prismatic forms {001} and {011} and having terminations possibly composed of the forms {100} and {611̄}. The mineral is transparent and has a white streak, subadamantine lustre, Mohs hardness of about 2½, brittle tenacity, irregular to splintery fracture, one perfect cleavage on {001} and possibly one or more additional cleavages parallel to [100]. Calciodelrioite is soluble in water. The calculated density is 2.451 g cm– 3. It is optically biaxial (+) with α = 1.733(3), β = 1.775(3), γ = 1.825(3) (white light), 2Vmeas = 87.3(9)° and 2Vcalc = 87°. The optical orientation is X = b; Z ≈ a. No pleochroism was observed. Electronmicroprobe analyses of two calciodelrioite samples and type delrioite provided the empirical formulae (Ca0.88Sr0.07Na0.04K0.01)Σ1.00(V1.00O3)2(H2.01O)4, (Ca0.76Sr0.21Na0.01)Σ0.98(V1.00O3)2(H2.01O)4 and (Sr0.67Ca0.32)Σ0.99(V1.00O3)2(H2.00O)4, respectively. Calciodelrioite is monoclinic, I2/a, with unit-cell parameters a = 14.6389(10), b = 6.9591(4), c = 17.052(2) Å, β = 102.568(9)°, V = 1695.5(3) Å3 and Z = 8. The seven strongest lines in the X-ray powder diffraction pattern [listed as dobs Å (I)(hkl)] are as follows: 6.450(100)(011); 4.350(16)(013); 3.489(18)(020); 3.215(17)(022); 3.027(50)(multiple); 2.560(28)(4̄15,413); 1.786(18)(028). In the structure of calciodelrioite (refined to R1 = 3.14% for 1216 Fo > 4σF), V5+O5 polyhedra link by sharing edges to form a zigzag divanadate [VO3] chain along a, similar to that in the structure of rossite. The chains are linked via bonds to Ca atoms, which also bond to H2O groups, yielding CaO3(H2O)6 polyhedra. The Ca polyhedra form a chain along b. Each of the two symmetrically independent VO5 polyhedra has two short vanadyl bonds and three long equatorial bonds. Calciodelrioite and delrioite are isostructural and are the endmembers of the series Ca(VO3)2(H2O)4–Sr(VO3)2(H2O)4. Calciodelrioite is dimorphous with rossite, which has a similar structure; however, the smaller 8-coordinate Ca site in rossite does not accommodate Sr.

Редкие сульфаты висмута каннонит Bi2O(SO4)(OH)2 и легернит Bi12.67O14(SO4)5 установлены нами в результате переизучения образцов висмутина из вольфрамового месторождения Букука (В. Забайкалье), хранящихся в систематической коллекции Минералогического музея им. А.Е. Ферсмана РАН под номером 56077. Оба минерала тесно срастаются между собой в составе полиминеральных псевдоморфоз по грубообразованным кристаллам висмутина, образуя прожилки длиной до 4 см и мощностью до 0.5 см. Эмпирические формулы: каннонит Bi2.06S0.97O5(OH)2, легернит Bi12.67S5.00O34. Параметры моноклинных элементарных ячеек: у каннонита a = 7.691(1), b = 13.874(2), c = 5.6569(8) Å, β = 109.23(1)°, V = 569.90(9) ų и Z = 4; у легернита: a = 11.197(2), b = 5.714(1), c = 11.879(2) Å, β = 99.37(2)°, V = 749.9(2) ų и Z = 1. Сильные полосы в КР-спектрах: у каннонита 111, 121, 144, 184, 221, 318, 437, 450, 560, 619, 983, 1059, 3439 см–1, у легернита 150, 183, 216, 313, 474, 969 см–1. Оба минерала найдены впервые на территории Российской Федерации.