Five celestine crystals were sampled from the (palaeo)surface intervening between the late Miocene to Pleistocene basaltic sequences of the Jabal Eghei (Nuqay) volcanic province in southern Libya and then characterised by applying a combination of the SEM–WDS, ICP/OES, PXRD and IR methods. Colour variations and related minerogenetic frameworks were also investigated. Three samples have greenish-blue-to-blue colour (480.4–482.5 nm), whereas the other two samples have blue–green colour (cyan; 489.1–494.1 nm). The colour purity ranges from 1.36–7.16. Their composition is similar, end-member celestine, in which only 1.6–4.1 at.% of Sr2+ content was substituted by Pb2+ (0.7–0.9 at.%), Ba2+ (0.5–0.7 at.%) and Ca2+ (0.2–0.8 at.%). Three samples contained vacancies, from 1.0 to 1.9 at.%. The content of other chemical elements is minor. The resulting unit-cell parameters have the ranges: a0 = 8.3578(9)–8.3705(6) Å; b0 = 5.3510(5)–5.3568(4) Å; c0 = 6.8683(7)–6.8767(2) Å and V0 = 307.17(5)–308.34(4) Å3. The PXRD and IR results are mainly in accordance with the SEM–WDS results, with a high level of correlation. However, a few discrepancies were found, producing several possible interpretations, the primary cause being a slight unit-cell axial anisotropy i.e. thermal expansion. As a consequence these results yield a new geothermometric tool that is based on the unit-cell axial anisotropy. The celestines investigated were formed during a Miocene intraplate volcanism with basaltic magmas, and associated brines lifted by the structural conduits (normal faults crosscutting the Sirt basin). The Sr-bearing fluids then poured into and over the faulted and fractured lagoon-type gypsum, anhydrite Eocene sediments. The celestine mineralisation formed within a ~368–430 K (~95–157°C) temperature range. The celestine formed at slightly elevated temperature and pressure conditions, close to the shallow subsurface environment (over 250 bars).
]]>Kalyuzhnyite-(Ce), ideally NaKCaSrCeTi(Si8O21)OF(H2O)3, is a new mineral from the Darai-Pioz alkaline massif, Tien-Shan mountains, Tajikistan. It occurs as equant grains up to 0.05 × 0.07 mm in a quartz–pectolite aggregate in a silexite-like peralkaline pegmatite. Associated minerals are quartz, fluorite, pectolite, baratovite, aegirine, leucosphenite, neptunite, reedmergnerite, orlovite, sokolovaite, mendeleevite-(Ce), odigitriaite, pekovite, zeravshanite, kirchhoffite and garmite. The mineral is colourless with a vitreous lustre and a white streak, and Dcalc. is 3.120 g/cm3. Kalyuzhnyite-(Ce) is monoclinic, P2/c, a = 18.647(4), b = 11.214(2), c = 14.642(3) Å, β = 129.55(3)° and V = 2360.9(11) Å3. The chemical composition of kalyuzhnyite-(Ce) is Nb2O5 0.53, TiO2 0.16, SiO2 43.85, Er2O3 0.13, Ho2O3 0.10, Gd2O3 0.09, Sm2O3 0.47, Nd2O3 6.22, Pr2O3 1.21, Ce2O3 6.34, La2O3 0.82, PbO 4.90, BaO 0.85, SrO 11.39, CaO 1.86, Cs2O 3.80, K2O 1.59, Na2O 2.99, H2O 5.24, F 1.55, O = F –0.65, total 100.31 wt.%. The empirical formula calculated on 26.11 (O + F) apfu is Na1.07K0.37Cs0.30Sr1.21Ca0.37Pb0.24Ba0.06(Ce0.43Nd0.41Pr0.08La0.06Sm0.03Gd0.01Er0.01Ho0.01)Σ1.04(Ti0.97Nb0.04)Σ1.01Si8.06O25.21F0.90H6.42, Z = 4. The simplified formula is (Na,□)(K,Сs)(Ca,Pb,Sr,Na)SrLn3+Ti(Si8O21)OF(H2O)3, where Ce is the dominant lanthanoid. The crystal structure was solved by direct methods and refined to an R1 index of 2.74%. In kalyuzhnyite-(Ce), the main structural units are a heteropolyhedral Na–Sr–Ce–Ti sheet, ideally [NaSrCeTiOF]7+, and a double (Si8O21)10– sheet parallel to (010). In the Si–O sheet, the Si tetrahedra form ten-membered rings. This is the first occurrence of such a double Si–O sheet in a mineral. The two sheets connect via common vertices of Na-, Sr-, Ce- and Ti-polyhedra and SiO4 tetrahedra to form a framework. The interstitial cations and H2O groups, ideally [(CaK)(H2O)3]3+, occur within the Si–O sheet. The mineral is named in honour of Vasily Avksentievich Kalyuzhny (1899–1993) in recognition of his contributions to the geology of ore deposits of Komi Republic (USSR) and the mineralogy of granitic pegmatites (Tajikistan).
]]>Okruginite, Cu2SnSe3 is a new mineral discovered from the high-sulfidation epithermal Au Ozernovskoye deposit, Kamchatka peninsula, Russia. It occurs as distinct Se-rich zones in Se-bearing mohite crystals or forms aggregates of small crystals 10–15 μm in size in quartz. In plane-polarised light, okruginite appears brownish grey. Pleochroism and bireflectance are discernible, anisotropy is weak, with rotation tints pale blue-grey to pale grey-brown; it exhibits no internal reflections. Reflectance values of the synthetic analogue of okruginite in air (R1, R2 in %) are: 25.9, 26.5 at 470 nm, 27.5, 26.5 at 546 nm, 27.8, 28.4 at 589 nm and 27.7, 28.4 at 650 nm. Twenty seven electron-microprobe analyses of okruginite give an average composition: Cu 29.48, Sn 28.10, Se 33.40 and S 8.75, total 99.73 wt.%, corresponding to the empirical formula Cu1.99Sn1.02(Se1.82S1.17)Σ2.99 based on 6 atoms; the average of seven analyses on its synthetic analogue is: Cu 23.62, Sn 24.37 and Se 49.09, total 97.08 wt.%, corresponding to Cu1.86Sn1.03Se3.11. The density, calculated on the basis of the empirical formula, is 5.126 g/cm3. The mineral is monoclinic, space group Cc, with a = 6.9906(2), b = 12.0712(4) Å, c = 6.9723(2) Å, β = 109.350(10)°, V = 555.1(2) Å3 and Z = 4. The crystal structure was solved and refined from the powder X-ray-diffraction data of synthetic Cu2SnSe3. Okruginite is the selenium-end member of the Cu2SnS3–Cu2SnSe3 solid solution. The mineral name is in honour of Dr. Victor Mikhailovich Okrugin, a Russian mineralogist, for his contributions to mineralogy and geology of epithermal deposits, in particular of the Au–Ag deposits in Kamchatka.
]]>Cotype material of stibiogoldfieldite from the Mohawk mine, Goldfield, Nevada, USA, has been examined in order to collect single-crystal X-ray diffraction data of Te-rich stibiogoldfieldite and to characterise the associated Ag–Bi–(S,Se) phase. Tellurium-rich stibiogoldfieldite, with empirical formula (Cu11.30Ag0.03)Σ11.33(Sb0.80As0.57Bi0.06Te2.57)Σ4.00(S12.83Se0.20)Σ13.03, is cubic, space group I3m, with unit-cell parameters a = 10.2947(3) Å and V = 1091.04(10) Å3. Its crystal structure has been refined to R1 = 0.0161 for 397 unique reflections with Fo > 4σ(Fo) and 25 refined parameters. The structure refinement confirmed the occurrence of a vacancy at the M(2) site, in agreement with the substitution M(2)Cu+ + X(3)(Sb/As)3+ = M(2)□ + X(3)Te4+. The Ag–Bi–(S,Se) phase was identified as the 6P homologue of the pavonite series, namely dantopaite. Its empirical formula is Cu1.36Ag4.39Pb0.12Bi12.62Sb0.06(S14.01Se7.91Te0.08), showing an exceptionally high Se content. Unit-cell parameters of Se-bearing dantopaite are a = 13.518(2), b = 4.0898(6), c = 18.984(3) Å, β = 106.816(6)°, V = 1004.7(3) Å3 and space group C2/m. The crystal structure was refined to R1 = 0.0504 for 1230 unique reflections with Fo > 4σ(Fo) and 82 refined parameters. The metal excess (~0.55 atoms per formula unit) of this pavonite homologue is mainly due to the accumulation of Ag and Cu in the thin slab of the crystal structure, whereas the high Se content is related to the partial replacement of S occurring preferentially in the thick PbS-like slab. Domains richer in Se and Pb in dantopaite, with empirical formula Cu0.89Ag4.50Pb0.49Bi12.53Sb0.07(S11.26Se10.74), were also identified, as grains up to 30 μm in size intimately intergrown with bohdanowiczite, indicating the possibility of a wide Se-to-S substitution in dantopaite.
]]>A new mineral cuprodobrovolskyite, ideally Na4Cu(SO4)3, was found in sublimates of the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with petrovite, saranchinaite, euchlorine, krasheninnikovite, langbeinite, calciolangbeinite, anhydrite, sanidine, tenorite and hematite. Cuprodobrovolskyite occurs as coarse hexagonal tabular or equant, typically skeletal crystals up to 1 mm and their clusters or crusts up to 1.5 cm × 2.5 cm in area. The mineral is transparent, light blue or greenish-bluish to almost colourless with vitreous lustre. Cuprodobrovolskyite is optically uniaxial (+) with ω = 1.509(3) and ε = 1.528(3). The empirical formula calculated on the basis of 12 O apfu is (Na3.64K0.09Pb0.03)Σ3.76(Cu0.51Ca0.22Mg0.16Zn0.07Al0.01Mn0.01)Σ0.98S3.04O12. The unit-cell parameters of cuprodobrovolskyite calculated from the powder X-ray diffraction data are: a = 15.702(2), c = 22.017(5) Å, V = 4701.0(2) Å3, space group R3 and Z = 18. The crystal structure was studied using the Rietveld method, Rp = 0.0246, Rwp = 0.0325, R1 = 0.0521 and wR2 = 0.0770. Cuprodobrovolskyite is an isostructural analogue of dobrovolskyite Na4Ca(SO4)3 with Cu prevailing over Ca. One of the main features of cuprodobrovolskyite is Cu2+ in 7-fold coordination. On the basis of relationships with saranchinaite Na2Cu(SO4)2 and petrovite Na12Cu2(SO4)8 in the Arsenatnaya fumarole and the results of heating experiments, cuprodobrovolskyite is considered as the highest-temperature phase among anhydrous Na–Cu sulfate minerals.
]]>Orthoamphibole, clinoamphibole and magnetite are common minerals in altered rocks associated spatially with Palaeoproterozoic volcanogenic massive sulfide (VMS) deposits in Colorado, USA and metamorphosed to the amphibolite facies. These altered rocks are dominated by the assemblage orthoamphibole (anthophyllite/gedrite)–cordierite–magnetite±gahnite±sulfides. Magnetite also occurs in granitoids, banded iron formations, quartz garnetite, and in metallic mineralisation consisting of semi-massive pyrite, pyrrhotite, chalcopyrite, and sphalerite with subordinate galena, gahnite and magnetite; amphibole also occurs in amphibolite. The precursor to the anthophyllite/gedrite–cordierite assemblages was probably the assemblage quartz–chlorite formed from hydrothermal ore-bearing fluids (~250° to 400°C) associated with the formation of metallic minerals in the massive sulfide deposits.
Element–element variation diagrams for amphibole, magnetite and ilmenite based on LA-ICP-MS data and Principal Component Analysis (PCA) for orthoamphiboles and magnetite show a broad range of compositions which are primarily dependent upon the nature of the host rock associated spatially with the deposits. Although discrimination plots of Al/(Zn+Ca) vs Cu/(Si+Ca) and Sn/Ga vs Al/Co for magnetite do not indicate a VMS origin, the concentration of Al+Mn together with Ti+V and Sn vs Ti support a hydrothermal rather than a magmatic origin for magnetite. Principal Component Analyses also show that magnetite and orthoamphibole in metamorphosed altered rocks and sulfide zones have distinctive eigenvalues that allow them to be used as prospective pathfinders for VMS deposits in Colorado. This, in conjunction with the contents of Zn and Al in magnetite, Zn and Pb in amphibole, ilmenite and magnetite, the Cu content of orthoamphibole and ilmenite, and possibly the Ga and Sn concentrations of magnetite constitute effective exploration vectors.
]]>Bimbowrieite, NaMgFe3+5(PO4)4(OH)6⋅2H2O, is a new mineral found in a mineralogically zoned rare-element bearing pegmatite at the White Rock No.2 quarry, Bimbowrie Conservation Park, South Australia, Australia. Crystals are dark olive green to greenish brown and are bladed with dimensions of up to 150 μm. Crystals occur as aggregates up to 0.4 mm across associated with ushkovite, bermanite, leucophosphite and sellaite. Bimbowrieite is pleochroic, biaxial (+), with α = 1.785(5), β = 1.795(5), γ = 1.805(5) and 2V(meas.) = 89.4(5)°. The average of 28 chemical analyses gave the empirical formula: (Na0.81Ca0.19)Σ1.00(Mg0.75Mn2+0.19Fe2+0.05)Σ0.99(Fe3+4.99Al0.01)Σ5.00(PO4)3.97(OH)5.88⋅2.05 H2O based on 24 oxygen atoms. Bimbowrieite is monoclinic, space group C2/c with a = 25.944(5), b = 5.1426(10), c = 13.870(3 Å, β = 111.60(3)°, V = 1720.4(7) Å3 and Z = 4. The crystal structure was refined to R1 = 1.97% for 1060 observed reflections with F0 > 4σ(F0). Bimbowrieite is isostructural with dufrénite. The structure is based on a trimer of face-sharing octahedra in which an M2 octahedra shares two trans faces with two M4 octahedra. Trimers link in the c-direction by sharing corners with two M3 octahedra and with T1 and T2 tetrahedra. Linkage in the a-direction is via corner-sharing M1 octahedra and linkage in the b-direction is via corner-sharing T1 and T2 tetrahedra.
]]>A new mineral species, guangyuanite, ideally Pb3Cl3(Se4+O3)(OH), was discovered from the El Dragón mine, Antonio Quijarro Province, Potosí Department, Bolivia. It occurs as equant crystals. Associated minerals are Co-bearing krut'aite–penroseite, chalcomenite, schmiederite, olsacherite, phosgenite, anglesite, cerussite and franksousaite. Guangyuanite is pale yellow–brown in transmitted light, transparent with white streak and vitreous lustre. It is brittle and has a Mohs hardness of ~3. No parting or cleavage was observed. The calculated density is 7.63 g/cm3. An electron microprobe analysis yielded an empirical formula [based on 7 (O + Cl) atoms per formula unit] of Pb3.02Cl3.01(Se4+0.99O3)(OH), which can be simplified to Pb3Cl3(Se4+O3)(OH).
Guangyuanite is isostructural with synthetic Pb3Br3(Se4+O3)(OH). It is orthorhombic, with space group Pnma and unit-cell parameters a = 11.0003(5), b = 10.6460(5), c = 7.7902 Å, V = 912.31(6) Å3 and Z = 4. The crystal structure of guangyuanite contains two symmetrically-distinct Pb (Pb1 and Pb2) cations, with Pb1 coordinated by eight anions (4O + 4Cl) and Pb2 only by six anions (3O + 3Cl), forming a marked lopsided coordination typical of Pb2+ with a stereochemically active 6s2 lone electron pair. The Se4+ cation forms a typical [Se4+O3] trigonal pyramid. The crystal structure of guangyuanite can be described as consisting of layers of edge-sharing [Pb1O4Cl4] polyhedra parallel to (100). These layers are linked together by sharing polyhedral corners (Cl atoms), as well as [Pb2O3Cl3] and [Se4+O3] groups. Chemically, guangyuanite is one of six lead chloride selenite minerals reported thus far and closely related to orlandiite Pb3Cl4(Se4+O3)⋅H2O.
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