A chemical and structural re-examination of fettelite samples from the type locality, Odenwald, southwest Germany

2012 ◽  
Vol 76 (3) ◽  
pp. 551-566 ◽  
Author(s):  
L. Bindi ◽  
R. T. Downs ◽  
P. G. Spry ◽  
W. W. Pinch ◽  
S. Menchetti

AbstractThe crystal structure and chemical composition of two samples of fettelite from the type locality, including a portion of the holotype material, was investigated to verify if a previously proposed revision of the chemical formula was applicable, and to study the role of cation substitution for Hg that would suggest new members of the fettelite family. The crystal structure of fettelite from the type locality was found to be equivalent to that reported previously for the Chilean occurrence, and consists of an alternation of two kinds of layers along c: layer A with general composition [Ag6As2S7]2– and layer B with general composition [Ag10HgAs2S8]2+. In this structure, the Ag atoms occur in various coordination configurations, varying from quasi-linear to quasi-tetrahedral, the AsS3 groups form pyramids as are typically observed in sulfosalts, and Hg links two sulfur atoms in a linear coordination. The refined compositions for the crystals in this study, [Ag6As2S7][Ag10(Fe0.53Hg0.47)As2S8] (R100124) and [Ag6As2S7][Ag10(Hg0.79Cu0.21)As2S8] (R110042), clearly indicate that new mineral species related to fettelite are likely to be found in nature.

2016 ◽  
Vol 80 (1) ◽  
pp. 175-186 ◽  
Author(s):  
Cristian Biagioni ◽  
Luca Bindi ◽  
Fabrizio Nestola ◽  
Ralph Cannon ◽  
Philippe Roth ◽  
...  

AbstractThe new mineral species ferrostalderite, CuFe2TlAs2S6, was discovered in the Lengenbach quarry, Binn Valley, Wallis, Switzerland. It occurs as minute, metallic, black, equant to prismatic crystals, up to 50 mu;m, associated with dolomite, realgar, baumhauerite (?) and pyrite. Minimum and maximum reflectance data for COM wavelengths in air are [λ (nm): R (%)]: 471.1: 24.2/25.4; 548.3: 23.7/24.7; 586.6: 22.9/23.8; 652.3: 21.0/22.0. Electron microprobe analyses give (wt.%): Cu 6.24(25), Ag 4.18(9), Fe 9.95(83), Zn 4.46(91), Hg 1.22(26), Tl 26.86(62), As 19.05(18), Sb 0.63(6),S 25.39(47), total 97.98(72). On the basis of 12 atoms per formula unit, the chemical formula of ferrostalderite is Cu0.75(2)Ag0.30(1)Fe1.36(10)Zn0.52(11)Hg0.05(1)Tl1.00(1)[As1.94(4)Sb0.04(1)]∑1.98(4)S6.04(4). The new mineral is tetragonal, space group I4̄2 m, with a = 9.8786(5), c = 10.8489(8) Å, V = 1058.71(11) Å3, Z = 4. The main diffraction lines of the calculated powder diagram are [d (in Å), intensity, hkl]: 4.092, 70, 211; 3.493, 23, 220; 3.396, 35, 103; 3.124, 17, 310; 2.937, 100, 222; 2.656, 19, 321; 2.470, 19, 400; 2.435, 33, 303. The crystal structure of ferrostalderite has been refined by Xray single-crystal data to a final R1= 0.050, on the basis of 1169 reflections with F0 > 4σ(F0). It shows a three dimensional framework of (Cu,Fe)-centred tetrahedra (1M1 + 2 M2), with channels parallel to [001] hosting disymmetric TlS6and (As,Sb)S3 polyhedra. Ferrostalderite is derived from its isotype stalderiteM1CuM2Zn2TlAs2S6through the homovalent substitution M2Zn2+ → M2Fe2+. The ideal crystal-chemical formula of ferrostalderite isM1CuM2Fe2TlAs2S6.


Minerals ◽  
2019 ◽  
Vol 9 (11) ◽  
pp. 702 ◽  
Author(s):  
Biagioni ◽  
Bindi ◽  
Mauro ◽  
Hålenius

The new mineral species scordariite, K8(Fe3+0.67□0.33)[Fe3+3O(SO4)6(H2O)3]2(H2O)11, was discovered in the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy. It occurs as pseudo-hexagonal tabular crystals, yellowish to brownish in color, up to 0.5 mm in size. Cleavage is perfect on {0001}. It is associated with giacovazzoite, krausite, gypsum, jarosite, alum-(K), and magnanelliite. Electron microprobe analyses give (wt %): SO3 47.31, Al2O3 0.66, Fe2O3 24.68, FeO 0.69, Na2O 0.52, K2O 17.36, H2Ocalc 15.06, total 106.28. The partitioning of Fe between Fe2+ and Fe3+ was based on Mössbauer spectroscopy. On the basis of 67 O atoms per formula unit, the empirical chemical formula is (K7.50Na0.34)Σ7.84(Fe3+6.29Al0.26Fe2+0.20)Σ6.75S12.02O50·17H2O. The ideal end-member formula can be written as K8(Fe3+0.67□0.33)[Fe3+3O(SO4)6(H2O)3]2(H2O)11. Scordariite is trigonal, space group R-3, with (hexagonal setting) a = 9.7583(12), c = 53.687(7) Å, V = 4427.4(12) Å3, Z = 3. The main diffraction lines of the observed X-ray powder pattern are [d(in Å), estimated visual intensity]: 8.3, strong; 6.6, medium; 3.777, medium; 3.299, medium; 3.189, medium; 2.884, strong. The crystal structure of scordariite has been refined using X-ray single-crystal data to a final R1 = 0.057 on the basis of 1980 reflections with Fo > 4σ(Fo) and 165 refined parameters. It can be described as a layered structure formed by three kinds of layers. As with other metavoltine-related minerals, scordariite is characterized by the occurrence of the [Fe3+3O(SO4)6(H2O)3]5− heteropolyhedral cluster.


Minerals ◽  
2020 ◽  
Vol 10 (11) ◽  
pp. 960
Author(s):  
Philippe Roth ◽  
Nicolas Meisser ◽  
Fabrizio Nestola ◽  
Radek Škoda ◽  
Fernando Cámara ◽  
...  

The new mineral species rüdlingerite, ideally Mn2+2V5+As5+O7·2H2O, occurs in the Fianel mine, in Val Ferrera, Grisons, Switzerland, a small Alpine metamorphic Mn deposit. It is associated with ansermetite and Fe oxyhydroxide in thin fractures in Triassic dolomitic marbles. Rüdlingerite was also found in specimens recovered from the dump of the Valletta mine, Canosio, Cuneo, Piedmont, Italy, where it occurs together with massive braccoite and several other As- and V-rich phases in richly mineralized veins crossing the quartz-hematite ore. The new mineral displays at both localities yellow to orange, flattened elongated prismatic, euhedral crystals measuring up to 300 μm in length. Electron-microprobe analysis of rüdlingerite from Fianel gave (in wt%): MnO 36.84, FeO 0.06, As2O5, 25.32, V2O5 28.05, SiO2 0.13, H2Ocalc 9.51, total 99.91. On the basis of 9 O anions per formula unit, the chemical formula of rüdlingerite is Mn1.97(V5+1.17 As0.83Si0.01)Σ2.01O7·2H2O. The main diffraction lines are [dobs in Å (Iobs) hkl]: 3.048 (100) 022, 5.34 (80) 120, 2.730 (60) 231, 2.206 (60) 16-1, 7.28 (50) 020, 2.344 (50) 250, 6.88 (40) 110, and 2.452 (40) 320. Study of the crystal structure showcases a monoclinic unit cell, space group P21/n, with a = 7.8289(2) Å, b = 14.5673(4) Å, c = 6.7011(2) Å, β = 93.773(2)°, V = 762.58(4) Å3, Z = 4. The crystal structure has been solved and refined to R1 = 0.041 on the basis of 3784 reflections with Fo > 4σ(F). It shows Mn2+ hosted in chains of octahedra that are subparallel to [-101] and bound together by pairs of tetrahedra hosted by V5+ and As5+, building up a framework. Additional linkage is provided by hydrogen-bonding through H2O coordinating Mn2+ at the octahedra. One tetrahedrally coordinated site is dominated by V5+, T(1)(V0.88As0.12), corresponding to an observed site scattering of 24.20 electrons per site (eps), whereas the second site is strongly dominated by As5+,T(2)(As0.74V0.26), with, accordingly, a higher observed site scattering of 30.40 eps. The new mineral has been approved by the IMA-CNMNC and named for Gottfried Rüdlinger (born 1919), a pioneer in the 1960–1980s, in the search and study of the small minerals from the Alpine manganese mineral deposits of Grisons.


2014 ◽  
Vol 78 (1) ◽  
pp. 101-117 ◽  
Author(s):  
C. Biagioni ◽  
E. Bonaccorsi ◽  
Y. Moëlo ◽  
P. Orlandi ◽  
L. Bindi ◽  
...  

AbstractThe new mineral species arsiccioite, AgHg2TlAs2S6, was discovered in the baryte-pyrite-iron oxide ore deposit exploited at the Monte Arsiccio mine, near Sant’Anna di Stazzema (Apuan Alps, Tuscany, Italy). It occurs as anhedral grains scattered in microcrystalline baryte, associated with cinnabar, laffittite, protochabournéite, pyrite, realgar, Hg-bearing sphalerite and stibnite. Arsiccioite is red, with a metallic to sub-metallic lustre. Minimum and maximum reflectance data for COM wavelengths in air are [λ (nm):R(%)]: 471.1: 29.0/29.4; 548.3: 27.6/28.3; 586.6: 26.1/26.5; 652.3: 24.2/24.6. Electron microprobe analyses give (wt.%): Cu 0.78(6), Ag 8.68(21), Zn 0.47(27), Fe 0.04(1), Hg 35.36(87), Cd 0.20(5), Tl 18.79(33), As 10.77(19), Sb 4.75(10), S 18.08(21), Se 0.07(5), total 97.99(44). On the basis of ΣMe= 6 a.p.f.u., the chemical formula is Ag0.87(2)Cu0.13(1)Zn0.08(4)Fe0.01(1)Hg1.91(5)Cd0.02(1)Tl1.00(2)(As1.56(2)Sb0.42(1))S1.98S6.12(6)Se0.01(1). Arsiccioite is tetragonal,I2m, witha10.1386(6),c11.3441(5) Å,V1166.1(2) Å3,Z= 4. The main diffraction lines of the powder diagram are [d(in Å), visually estimated intensity,hkl]: 4.195, m, 211; 3.542, m, 103; 3.025, vs, 222; 2.636, m, 114; 2.518, s, 400 and 303. The crystal structure of arsiccioite has been refined by single-crystal X-ray data to a finalR1= 0.030, on the basis of 893 observed reflections. It shows a three dimensional framework of (Hg,Ag)- centred tetrahedra (1M1 + 2M2), with channels parallel to [001] hosting TlS6and (As,Sb)S3 disymmetric polyhedra. Arsiccioite is derived from its isotype routhieriteM1CuM2Hg2TlAs2S6through the double heterovalent substitutionM1Cu++M2Hg2+→M1Hg2++M2Ag+. This substitution obeys a steric constraint, with Ag+, the largest cation relative to Hg2+and Cu+, entering the largestM2 site. The ideal crystal chemical formula of arsiccioite isM1HgM2(Hg0.5Ag0.5)2TlAs2S6. The crystal chemistry of the routhierite isotypic series is discussed. Finally, the distribution of Hg ore minerals in the Apuan Alps is reviewed.


2013 ◽  
Vol 77 (7) ◽  
pp. 3027-3037 ◽  
Author(s):  
C. Biagioni ◽  
P. Orlandi ◽  
F. Nestola ◽  
S. Bianchin

AbstractThe new mineral species oxycalcioroméite, Ca2Sb5+2O6O, has been discovered at the Buca della Vena mine, Stazzema, Apuan Alps, Tuscany, Italy. It occurs as euhedral octahedra, up to 0.1 mm in size, embedded in dolostone lenses in the baryte + pyrite + iron oxides ore. Associated minerals are calcite, cinnabar, derbylite, dolomite, hematite, 'mica', pyrite, sphalerite and 'tourmaline'. Oxycalcioroméite is reddish-brown in colour and transparent. It is isotropic, with ncalc = 1.950.Electron microprobe analysis gave (wt.%; n = 6) Sb2O5 63.73, TiO2 3.53, SnO2 0.28, Sb2O3 10.93, V2O3 0.68, Al2O3 0.28, PbO 0.68, FeO 5.52, MnO 0.13, CaO 13.68, Na2O 0.83, F 1.20, O = F – 0.51, total 100.96. No H2O, above the detection limit, was indicated by either infrared or micro-Raman spectroscopies. The empirical formula, based on 2 cations at the B site, is (Ca1.073Fe2+0.338Sb3+0.330Na0.118Pb0.013Mn0.008)Σ=1.880(Sb5+1.734Ti0.194V0.040Al0.024Sn0.008)Σ=2.000(O6.682F0.278)Σ6.960. The crystal structure study gives a cubic unit cell, space group Fdm, with a 10.3042(7) Å, V 1094.06(13) Å3, Z = 8. The five strongest X-ray powder diffraction lines are [d(Å)I(visually estimated)(hkl)]: 3.105(m)(311); 2.977(s)(222); 2.576(m)(400); 1.824(ms)(440); and 1.556(ms)(622). The crystal structure of oxycalcioroméite has been solved by X-ray single-crystal study on the basis of 114 observed reflections, with a final R1 = 0.0114. It agrees with the general features of the members of the pyrochlore supergroup.


2019 ◽  
Vol 104 (12) ◽  
pp. 1851-1856 ◽  
Author(s):  
Anthony R. Kampf ◽  
John M. Hughes ◽  
Barbara P. Nash ◽  
Joe Marty

Abstract Bicapite, KNa2Mg2(H2PV145+O42)·25H2O, is a new mineral species (IMA2018-048) discovered at the Pickett Corral mine, Montrose County, Colorado, U.S.A. Bicapite occurs as square tablets up to about 0.2 mm on edge on montroseite-corvusite-bearing sandstone. Crystals are dark red-brown, often appearing black. The streak is orange, and the luster is vitreous. Bicapite is brittle, has a Mohs hardness of 1½, and displays one excellent cleavage on {100}. The measured density is 2.44(2) g/cm3. Bicapite is uniaxial (+), ω = 1.785(5), ε ≈ 1.81 (white light); pleochroism is red-brown; E > O, slight. The electron probe microanalysis and results of the crystal structure determination provided the empirical formula (based on 67 O apfu) (K1.23Na2.23Mg1.48)Σ4.94[H2.51P1.02(V13.915+Mo0.076+)Σ13.98O42]·25H2O. Bicapite is tetragonal, I4/m, with a = 11.5446(12) Å, c = 20.5460(14) Å, V = 2738.3(6) Å3, and Z = 2. The strongest four lines in the diffraction pattern are [d in Å (I) (hkl)]: 10.14 (100) (002,101); 2.978 (29) (134,206); 2.809 (11) (305); and 2.583 (11) (420,008). The atomic arrangement of bicapite was solved and refined to R1 = 0.0465 for 1008 independent reflections with I > 2σI. The structural unit is a [H2PV125+O40(V5+O)2]7– heteropolyanion composed of 12 distorted VO6 octahedra surrounding a central PO4 tetrahedron and capped on opposite sides by two VO5 square pyramids; the structural unit is a modification of the α-isomer of the Keggin anion, [XM12O40]n–. Charge balance in the structure is maintained by the [KNa2Mg2(H2O)25]7+ interstitial complex. The name bicapite is in recognition of this being the only known mineral with a structure based on a bicapped Keggin anion. The discovery of bicapite and numerous other natural polyoxometalate compounds in the Colorado Plateau uranium/vanadium deposits make that the most productive region found to date for naturally occurring polyoxometalate compounds.


2020 ◽  
Vol 58 (3) ◽  
pp. 381-394
Author(s):  
Leonid A. Pautov ◽  
Mirak A. Mirakov ◽  
Fernando Cámara ◽  
Elena Sokolova ◽  
Frank C. Hawthorne ◽  
...  

ABSTRACT Badakhshanite-(Y), ideally Y2Mn4Al(Si2B7BeO24), is a tetrahedral sheet-structure mineral found in the Dorozhny (Road) miarolitic granitic pegmatite within the Kukurt pegmatite field 45 km E of Murghab, Eastern Pamir, Gorno-Badakhshan Autonomous Oblast, Tajikistan. Badakhshanite-(Y) occurs in medium- to coarse-grained non-graphic albite-microcline-quartz pegmatites in close association with smoky quartz, Sc-bearing spessartine, Sc-bearing tusionite, and schorl. It often grows together with Sc-bearing tusionite and occurs as single columnar crystals ranging from 50 to 400 μm in length, as inclusions in spessartine and tourmaline, and rarely as crystals in blebs along boundaries between garnet, tourmaline, and quartz. Badakhshanite-(Y) is yellow brown and has a white streak and a vitreous luster. It is brittle, with a conchoidal fracture, Mohs hardness of 6.5–7, and calculated density of 4.41 g/cm. In thin section it is transparent and pale yellow, non-pleochroic, biaxial (–), with α = 1.805(2), βcalc = 1.827, γ = 1.835(3) (λ = 590 nm); 2V (meas.) = –60(10)°. Dispersion is weak, r > v. Extinction is straight, elongation is negative. FTIR spectra show the absence of (OH) and H2O groups. Chemical analysis by electron microprobe using WDS (6 points), SIMS, and ICP-OES for B and Be gave SiO2 11.96, ThO2 0.12, Sm2O3 0.17, Gd2O3 0.30, Tb2O3 0.10, Dy2O3 0.73, Ho2O3 0.19, Er2O3 1.34, Tm2O3 0.54, Yb2O3 8.82, Lu2O3 2.32, Y2O3 16.60, Sc2O3 1.57, Al2O3 3.06, B2O3 22.06, FeO 0.94, MnO 23.33, CaO 0.58, BeO 2.84, total 97.57 wt.%.The empirical formula based on 24 O apfu is (Y1.21REE0.78Th0.01)Σ2(Mn3.47Y0.34Ca0.11Fe2+0.08)Σ4(Al0.63Sc0.24Fe2+0.06□0.07)Σ1[(Si2.10B6.69Be1.20)Σ9.99O24], where REE = (Yb0.47Lu0.12Dy0.04Er0.07Tm0.03 Ho0.01Gd0.02Sm0.01Tb0.01)Σ0.78. Badakhshanite-(Y) is orthorhombic, space group Pnma, a 12.852(1), b 4.5848(5), c 12.8539(8) Å, V 757.38(7) Å3, Z = 2. The crystal structure was refined to R1 = 4.31% based on 1431 unique [F > 4σF] reflections. In the crystal structure of badakhshanite-(Y), a layer of tetrahedra parallel to (010) is composed of four different tetrahedrally coordinated sites: Si, B(1), B(2), and T (<Si–O> = 1.623 Å, <B(1)–O> = 1.485 Å, <B(2)–O> = 1.479 Å, <T–O> = 1.557 Å), which form four-, five-, and eight-membered rings, having the composition (Si2B7BeO24). Between the sheets of tetrahedra, there are three cation sites: M(1), M(2), and M(3) (<M(1)–O> = 2.346 Å, <M(2)–O> = 2.356 Å, <M(3)–O> = 2.016 Å) occupied by Y(REE), Mn2+(Y, Ca, Fe2+), and Al(Sc), respectively. The M(1,2) sites ideally give Y2Mn4apfu; the M(3) site ideally gives Al apfu. Badakhshanite-(Y) is an Al- and Be-analogue of perettiite-(Y).


1990 ◽  
Vol 54 (376) ◽  
pp. 495-500 ◽  
Author(s):  
Jan T. Szymański ◽  
Andrew C. Roberts

AbstractThe crystal structure of the new mineral voggite, Na2Zr(PO4)(CO3)(OH).2H2O , from the Francon quarry, Montreal, Quebec, Canada, has been solved in order to determine the correct chemical formula, as conventional electron microprobe methods were found unreliable. The unit cell is monoclinic, I2/m, with a = 12.261(2), b = 6.561(1), c = 11.757(2)Å, β = 116.19(2)°. The structure consists of layers of edge-sharing Zr-O pentagonal bipyramids, separated by layers of Na-(O,H2O) octahedra. The carbonate ion acts as a bidentate ligand in the Zr-O polyhedron, the third oxygen atom being bonded to the Na atom. The phosphate group is bonded to three different Zr atoms and to a Na atom. The Zr-O bond lengths vary from 2.067 to 2.283 (mean 2.140Å), while Na-O are between 2.304 and 2.773, (σ = 0.006Å, mean 2.480Å). The carbonate and phosphate bonds are normal. It is inferred from the structure that the columns of octahedrally coordinated Na atoms can easily be broken apart when subjected to the heat generated by the electron microprobe beam, with the subsequent expulsion of water. This gives rise to ‘mobile’ Na atoms, which make quantitative electron microprobe analysis extremely difficult. The structure allows the ‘liberated’ Na atoms to move freely within planes parallel to .


2012 ◽  
Vol 76 (5) ◽  
pp. 1247-1255 ◽  
Author(s):  
R. W. Turner ◽  
O. I. Siidra ◽  
S. V. Krivovichev ◽  
C. J. Stanley ◽  
J. Spratt

AbstractRumseyite, ideally [Pb2OF]Cl, is a new mineral species which is associated with calcite, cerussite, diaboleite, hydrocerussite and undifferentiated Mn oxides in a small cavity in 'hydrocerussite' from a manganese pod at Merehead quarry, Somerset, England. Rumseyite is tetragonal, I4/mmm, a = 4.065(1), c = 12.631(7) Å, V = 208.7(1) Å3, Z = 2. The mineral is translucent pale orange-brown with a white streak and vitreous lustre. It is brittle with perfect {100} cleavage; Dcalc = 7.71 g cm–3 (for the ideal formula, [Pb2OF]Cl). The mean refractive index in air at 589 nm is 2.15. The six strongest reflections in the X-ray powder-diffraction pattern [dmeas in Å, (Irel), (hkl)] are as follows: 2.923(100)(013), 2.875(68)(110), 3.848(41)(011), 6.306(17)(002), 1.680(14)(123), 2.110(12)(006). The crystal structure of rumseyite is based on alternating [OFPb2] and Cl layers. Rumseyite is related to other layered Pb oxyhalides. Fluorine and oxygen are statistically disordered over one crystallographic site. Rumseyite is named in honour of Michael Scott (Mike) Rumsey (1980– ), Curator and Collections Manager at the NHM (London), who discovered the mineral. The mineral and name have been approved by the IMA Commission on New Mineral Names and Classification (IMA 2011-091). The holotype specimen is in the collections of the Natural History Museum, London (specimen number BM1970,110).


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