Dan Topa

A new mineral, chrisstanleyite, Ag2Pd3Se4, from Hope's Nose, Torquay, Devon, England

Abstract Chrisstanleyite, Ag2Pd3Se4, is a new mineral from gold-bearing carbonate veins in Middle Devonian limestones at Hopes Nose, Torquay, Devon, England. It is associated with palladian and argentian gold, fischesserite, clausthalite, eucairite, tiemannite, umangite, a Pd arsenide-antimonide (possibly mertieite II), cerussite, calcite and bromian chlorargyrite. Also present in the assemblage is a phase similar to oosterboschite, and two unknown minerals with the compositions, PdSe2 and HgPd2Se3. Chrisstanleyite occurs as composite grains of anhedral crystals ranging from a few lam to several hundred μm in size. It is opaque, has a metallic lustre and a black streak, VHN100 ranges from 371-421, mean 395 kp/mm2 (15 indentations), roughly approximating to a Mohs hardness of 5. Dcalc = 8.308 g/cm3 for the ideal formula with Z = 2. In plane-polarised reflected light, the mineral is very slightly pleochroic from very light buff to slightly grey-green buff, is weakly bireflectant and has no internal reflections. Bireflectance is weak to moderate (higher in oil). Anisotropy is moderate and rotation tints vary from rose-brown to grey-green to pale bluish grey to dark steel-blue. Polysynthetic twinning is characteristic of the mineral. Reflectance spectra and colour values are tabulated. Very little variation was noted in eleven electron-microprobe analyses on five grains, the mean is: Ag 25.3, Cu 0.17, Pd 37.5, Se 36.4, total 99.37 wt.%. The empirical formula (on the basis of ∑M + Se = 9) is (Ag2.01Cu0.02)∑2.03 Pd3.02Se3.95, ideally Ag2Pd3Se4 . Chrisstanleyite is monoclinic, a 6.350(6), b 10.387(4), c 5.683(3) Å, β 114.90(5)° space group P21/m (11) or P21(4). The five strongest X-ray powder-diffraction lines [d in Å (I)(hkl)] are: 2.742 (100) (-121), 2.688 (80) (-221), 2.367 (50) (140), 1.956 (100) (-321,150) and 1.829 (30) (-321,042). The name is in honour of Dr Chris J. Stanley of The Natural History Museum in London. The mineral and its name have been approved by the Commission on New Minerals and Mineral Names of the International Mineralogical Association.

Another step toward understanding the true nature of sartorite: Determination and refinement of a ninefold superstructure

Abstract Single-crystal X-ray diffraction data, collected from a sartorite crystal from Lengenbach (Binntal, Valais, Switzerland), yielded a ninefold superstructure: space group P21/c; a = 37.71(2), b = 7.898(3), c = 20.106(8) Å, β = 101.993(7)°; R1 = 6.08% for 6293 reflections with I > 2σI. The sample is an N1,2 = 3,3 sartorite homologue and the refined formula Pb8Tl1.5As17.5S35 compares very well with the empirical formula Pb8.2Tl1.4As17.5Sb0.5S35 obtained from electron microprobe analyses. It has a high Tl content, up to 6.5 wt%. In a coupled substitution approximately 1.5 Tl+ replace about 0.5 As3+ and 1 PbS. The refined structure has 35 S atoms pfu instead of the expected 36 S (= 9 × 4 S, from PbAs2S4). The incorporation of substantial amounts of Tl+ into PbAs2S4 is essential for the type and periodicity of superstructures in sartorite. The refined superstructure can be interpreted as a socalled “lock-in” structure with a composition that yields a commensurate lattice for a mineral that usually has an incommensurate lattice. No commensurate periodicity could be found for a second crystal with about 0.5 Tl apfu.

Verbeekite, monoclinic PdSe2, a new mineral from the Musonoi Cu-Co-Mn-U mine, near Kolwezi, Shaba Province, Democratic Republic of Congo

Abstract Verbeekite, ideally PdSe2, monoclinic with space-group choices C2/m, C2 or Cm; a = 6.659(7), b = 4.124(5), c = 4.438(6) Å, β = 92.76(3)8, V = 121.7(4) Å3; a:b:c = 1.6147:1:1.0761, Z = 2, is a new, very rare, primary mineral, intimately associated with secondary oosterboschite {(Pd,Cu)7Se5}, from the Musonoi Cu-Co-Mn-U mine, near Kolwezi, Shaba Province, Democratic Republic of Congo. Additional associated minerals are Cu- and Pd-bearing trogtalite {(Co,Cu,Pd)Se2}, Se-bearing digenite and Se-bearing covellite. The strongest five lines of the X-ray powder-diffraction pattern {d in Å (I) (hkl)} are: 4.423(30)(001), 3.496 (30)(110), 2.718(100)(111), 1.955(50)(310) and 1.896(50)(1̄12). The mineral has also been identified, as a single anhedral 25 μm-sized grain, from Hope’s Nose, Torquay, Devon, England where it is associated with native gold, chrisstanleyite Ag2Pd3Se4, oosterboschite(?), unnamed Pd2HgSe3 and cerussite. At Musonoi, altered verbeekite grains do not exceed 200 μm in size and are anhedral, black, with a black streak and a metallic lustre. The mineral is opaque, brittle, has an uneven fracture, and lacks discernible cleavage. The VHN5 ranges 490-610, mean 550 kp/mm2 (2 indentations), roughly approximating a Mohs’ hardness of 5Ý. Dcalc. = 7.211 g/cm3 for the ideal formula. Electron-microprobe analyses (mean of 4 spot analyses) yielded Pd 39.6, Cu 0.5, Se 58.8, total 98.9 wt.%. The empirical formula is (Pd0.99Cu0.02)∑1.01Se1.99, based on Pd+Cu+Se = 3. In plane-polarized reflected light, the mineral is a nondescript grey and is neither pleochroic nor perceptibly bireflectant. Anisotropy is moderate with rotation tints in varying shades of brown. Reflectance spectra and colour values are tabulated. The name honours Dr Théodore Verbeek (1927-1991) who was the first geoscientist to study the Musonoi palladium mineralization in the Democratic Republic of Congo (1955-1967) and who co-discovered this new mineral phase.

The new mineral baumstarkite and a structural reinvestigation of aramayoite and miargyrite

Abstract Baumstarkite is a new mineral found coating miargyrite from the San Genaro mine, Huancavelica Department, Peru. It is triclinic and the third naturally occurring modification of AgSbS2 besides monoclinic miargyrite and cubic cuboargyrite. The composition is usually close to the ideal formula. However, some grains of baumstarkite show zoned lamellae with As contents up to 11.5 wt% and accords to Ag3(Sb,As)2SbS6. Baumstarkite is isotypic with aramayoite [end-member composition Ag3Sb2BiS6; solid solutions require the extended formula Ag3Sb2(Bi,Sb)S6]. Single-crystal X-ray structure investigations were performed for baumstarkite [type locality, a = 7.766(2), b = 8.322(2), c = 8.814(2) Å, α = 100.62(2), β = 104.03(2), γ = 90.22(2)°, Z = 2{Ag3Sb3S6}, space group P1̅, R1(F) = 0.057, wR2(F2) = 0.128], aramayoite [Armonia mine, El Quevar, Argentinia: a = 7.813(2), b = 8.268(2), c = 8.880(2) Å, α = 100.32(2), β = 104.07(2), γ = 90.18(2)°, Z = 2{Ag3Sb2S6}, space group P1̅, R1(F) = 0.034, wR2(F2) = 0.084], and miargyrite associated with baumstarkite type material [a = 12.862(3), b = 4.409(1), c = 13.218(3) Å, β = 98.48(2)°, Z = 8{AgSbS2}, space group C2/c, R1(F) = 0.031, wR2(F2) = 0.082]. The space-group symmetries of aramayoite and miargyrite were revised, and the refinements unambiguously showed that the three investigated minerals are centrosymmetric. In baumstarkite and aramayoite each three atomic sites are occupied by Ag and M = As, Sb, Bi, respectively. The Ag atoms have two short bonded ligands (Ag-S is 2.51 to 2.58 Å). The M1 and M2 sites are [3 + 3] coordinated and are predominantly occupied by (Sb, As) atoms (M-S = 2.44 to 2.54 Å and > 3.09 Å). The [2 + 2 + 2] coordination of the M3 atom differs in the two mineral species: the two shortest bond lengths in baumstarkite are smaller (2.51 Å) than in aramayoite (2.64 Å) to allow for the different sizes of the Sb and Bi atoms, respectively; the medium bond lengths are similar (2.75 to 2.82 Å) and the longest bond lengths are > 3.02 Å. Considering only the nearest-neighbor environments, baumstarkite and aramayoite feature zigzag chains parallel to [010], which are linked together to form layers parallel to (001). In miargyrite [2 + 2] and [2] coordinated Ag atoms are linked by SbS3 pyramids to form a three-dimensional network.

Twinnite, Pb0.8Tl0.1Sb1.3As0.8S4, the OD character and the question of its polytypism

Abstract The electron-microprobe analyses of the studied twinnite material from Jas Roux, France, show a uniform chemical composition Pb0.80Tl0.05Sb1.31As0.80S4.04. Twinnite is monoclinic; the space group is P21/n. Lattice parameters obtained from single-crystal diffractometer data are a = 7.997(2) Å, b = 19.517(5) Å, c = 8.634(2) Å, and β = equal to 91.061(4)°. The structure of twinnite contains two distinct Pb sites, two Sb positions, two mixed-occupancy (As,Sb) positions and eight anions. The short (Sb,As)—S bonds are arranged into crankshaft chains. Twinnite is a N = 3 member of the sartorite homologous series. It is related to guettardite which has different symmetry and a substantially different Sb : As ratio. These two compounds are configurational polytypes, with unit OD layers having layer group symmetry P21(n)m and P-1 in terms of twinnite lattice.

Crystal structure of a synthetic tin-selenium representative of the cylindrite structure type

Abstract The synthetic tin-selenium member of the cylindrite structural family, with the empirical formula Sn31.52Sb6.23Fe3.12S59.12 based on electron-microprobe data, has a triclinic crystal structure composed of two alternating layer types, both with a pronounced one-dimensional modulation, and with a noncommensurate layer match in two dimensions. The pseudotetragonal (Q) layer is a MeSe layer twoatomic planes thick with lattice parameters a = 5.969(2) Å, b = 6.004(1) Å, and the layer-stacking vector c = 12.238(1) Å, α = 87.98(4)°, β = 83.14(3)°, and γ = 90.01(4)°. The pseudohexagonal (H) layer is a single-octahedral MeSe2 layer with a = 3.831(1) Å, b = 6.580(3) Å, c = 12.151(5) Å, α = 87.79(4)°, β = 90.59(3)°, and γ = 89.99(3)°; the a and b vectors of the two subsystems are parallel, the c vectors diverge. The transversal wave-like modulation has the wave-normal parallel to b, so that the modulation vector q is 0.0001(3) a* + 0.1921(4) b* - 0.0119(3) c* in terms of the pseudohexagonal subsystem. Superspace structure refinement in the superspace group X1̄ where X stands for non-primitive centering vectors (½,½,0,0,0), (0,0,0,0,½), (½,½,0,0,½) in five-dimensional superspace, and based on 2128 observed reflections, resulted in R1 = 0.038 for all reflections. Composition of the H layer has been modeled as Sn4+240Fe2+54Se588, that of the Q layer as Sn2+306Sb3+108Se414. The cation-anion distances in the Q layer vary between 2.63 and 3.30 Å, indicating that the cations present are primarily Sn2+ (and Sb3+), whereas distances in the H layer lie between 2.665 and 2.721 Å and correspond to Sn4+ with admixture of Fe2+. The shortest cation-anion distance across the interlayer space is 3.24 Å. Relations between layer match and the modulation vector, divergence of layer stackings of the two components, and reasons for the modulation and for the pronounced disorder of the Q component, as well as the differences and similarities with levyclaudite, franckeite, and synthetic layer-misfit compounds are discussed in detail. In its structural principles, although not in numerical values, the Sn-Se cylindrite corresponds fully to the natural Pb-Sn-S cylindrite previously described.

The crystal structure of synthetic buckhornite, (Pb2BiS3)(AuTe2)

Synthetic buckhornite, [Pb2BiS3][AuTe2], was grown from melts in connection with the search for high-temperature superconductive materials. Chemical analyses were performed by electron-microprobe investigations. The crystal structure was determined from 726 single-crystal X-ray reflections of a twinned crystal. The refinement gave R(F)=0.101 for 33 variable parameters. The space group is Pmmn, a=4.108(3) Å, b=12.308(9) Å, c=9.331(6) Å, Z=2. The atomic arrangement features a pronounced layer structure formed by two different sheets. (a) Planar Au[4Te]Te4 configurations are edge-connected to ribbons in [100]; they are linked by Te···Te contacts to planar nets parallel to (001). Te and Au atoms are in a distorted square arrangement. (b) Slices of (Pb,Bi)S are sandwiched between these AuTe2 layers. They form SnS-archetype layers. The present paper proves that buckhornite, [(Pb2Bi)Σ3S3] [(Te2Au)Σ3], and nagyagite, [(Pb3(Pb,Sb)3)Σ6S6][(Te,Au)3] are members of a homologous series. Both compounds have comparable Au—Te layers. However, ordering of Au and Te atoms was verified in buckhornite only. In buckhornite two (Pb,Bi)S sheets form one slice of the SnS-archetype whereas in nagyagite four (Pb,Sb)S layers form the corresponding slice with a thickness of two SnS-archetype slabs.

The crystal structure of gustavite, PbAgBi 3 S 6 Analysis of twinning and polytypism using the OD approach

The crystal structure of gustavite Pb 1.06 Ag 0.95 Bi 2.80 Sb 0.20 S 5.99 from Rotgulden, Lungau, Salzburg Land, Austria, was refined to R 1 = 2.76 % using single-crystal X-ray diffraction data. Refined unit-cell parameters are a 7.0567(14), b 19.6905(39), c 8.2219(16) A, β 106.961(3) °, unit-cell volume 1092.7(2) A 3 and space group is P 2 1 /c . The structure contains a bicapped trigonal prismatic Pb site, a [001] string of Ag and Bi 1 octahedral sites and a similar string of Bi 2 and Bi 3 coordination octahedra. Sb is concentrated in the Bi 3 site whereas Bi 1 and Ag contain a fraction (0.1–0.14 atom) of the opposite species; the latter is explained by a presence of twin lamellae or antiphase domains in the crystal. In accordance with its frequently observed twinning, gustavite is an OD (order-disorder) structure that can be described by zig-zag unit layers with layer symmetry P (2 /n ) 2 1 / c 2/ m and the interlayer symmetry elements {(2 2 / n 1,1/2 ) 2 1 / n 1/2,2 2 1/2 / a 2 }. An alternative OD description uses planar unit layers with the layer symmetry P (2/ b ) 2 1 / c 2 1 / m and the interlayer elements 2 2 / n 1,−1/2 2 1 / n 1/2,2 2 1/2 / a 2 . The former description adheres closely to the details of coordination of bismuth observed in the structure whereas the latter description is based on a more abstract structure model.

The crystal structure of franckeite, Pb21.7Sn9.3Fe4.0Sb8.1S56.9

Abstract The layer-like crystal structure of franckeite from the mine of San José, Bolivia, exhibits a pronounced one-dimensional transversal wave-like modulation and a non-commensurate layer match in two dimensions. It consists of alternating pseudohexagonal (H) layers and pseudotetragonal (Q) slabs and forms a homologous pair with cylindrite, which has thinner Q slabs. The Q slabs in franckeite are four atomic layers thick. The two components have their own lattices and a common modulation. The Q slab of the refined franckeite structure, Pb21.74Sn9.34Fe3.95Sb8.08S56.87, is an MS layer (M = Pb2+, Sn2+, Sb3+) four atomic planes thick, with a = 5.805(8), b = 5.856(16) Å, and the layer-stacking vector c = 17.338(5) Å. The lattice angles are α = 94.97(2)°, β = 88.45(2)°, γ = 89.94(2)°; the modulation vector q = -0.00129(8) a* + 0.128436(10) b* - 0.0299(3) c*. The H layer is a single-octahedron MS2 layer (M = Sn4+, Fe2+) with a = 3.665(8), b = 6.2575(16), c = 17.419(5) Å, α = 95.25(2)°, β = 95.45(2)°, γ = 89.97(2)°; the modulation vector is q = -0.00087(8) a* + 0.13725(16) b* - 0.0314(4) c*. The a and b vectors of both subsystems are parallel; the c vectors diverge. (3+2)D superspace refinement was performed in the superspace group C1, using 7397 observed reflections. It resulted in the overall R(obs) value equal to 0.094. The Q slabs are composed of two tightly bonded double-layers, separated by an interspace hosting non-bonding electron pairs. Average composition of cations on the outer surface was refined as Pb0.74(Sn,Sb)0.26, whereas that of cations, which are adjacent to the interspace with lone electron pairs, with a configuration analogous to that observed in orthorhombic SnS, corresponds to (Sn,Sb)0.73Pb0.27. Iron is dispersed over the octahedral Sn4+ sites in the H layer. Transversal modulation of the Q slab is achieved by local variations in the Pb:(Sn,Sb) ratios at its surface and interior. Its purpose is to re-establish a one-dimensional commensurate contact along [010] between the curved Q and H surfaces to the greatest extent possible. Layer-stacking disorder and divergence of the Q and H stacking directions, and the divergence between modulation wave-front and these stacking directions are typical for the composite structures of franckeite and cylindrite. Because of the increased rigidity of the Q component, franckeite usually forms masses of curved crystals rather than cylindrical aggregates. The existence of this family depends critically on the radius ratios of the cations involved, especially those involving (Pb2+, Sn2+) and Sn4+. Their replacement by a Pb2+:Bi3+ combination leads to misfit layer structures of a very different type, typified by cannizzarite.

Suredaite, PbSnS3, a new mineral species, from the Pirquitas Ag-Sn deposit, NW-Argentina: mineralogy and crystal structure

Abstract Suredaite, ideally PbSnS3, is a new mineral species from the Pirquitas Ag-Sn deposit (Province Jujuy, NW-Argentina). It was observed in symmetrically banded veins in the Oploca district, and is associated with sphalerite, arsenopyrite, pyrite-marcasite, cassiterite, cylindrite, franckeite, hocartite, rhodostannite, and various Ag-Sb and Ag-Bi sulfosalts in minor amounts. Suredaite occurs in layers up to 1 cm in thickness as aggregates of radially arranged tabular-prismatic (single) crystals, has a metallic lustre, and a dark grey streak. VHN50 ranges between 18.2 and 20.6 (mean 19.6) GPa, the Mohs hardness is 2.5-3. It has perfect cleavages parallel to {001}, {101}, and {100}. The measured density varies between 5.54 and 5.88 g/cm3, Dx was determined to be 5.615 g/cm3. In reflected plane-polarised light, it is white and is not perceptibly bireflectant or pleochroic. It lacks internal reflections and is weakly anisotropic with metallic blue, mauve to brown rotation tints. Specular reflectance percentages in air and in oil are tabulated from 400 to 700 nm and compared graphically with those for the type specimen of teallite, PbSnS2. Electron microprobe analyses showed suredaite to be chemically inhomogeneous with respect to the compositional variations (in wt%): Pb 42.3- 48.5, Ag 0.3-1.1, Fe 0.3-1.0, As 0.2-2.1, Sn 27.7-30.2, S 23.1-24.7. The crystal structure determined from single-crystal X-ray diffraction data revealed orthorhombic symmetry [space group Pnma, Z = 4, a = 8.8221(3), b = 3.7728(3), c = 14.0076(3) Å; V = 466.23(4) Å3]. The atomic arrangement is isostructural to the NH4CdCl3 structure type which exists in a series of isotypic sulfides and selenide compounds. The suredaite structure, which is the natural analogue of synthetic PbSnS3, consists of columns of double-edge sharing octahedra running parallel to the b axis, which house the Sn atoms. These columns are linked by rods of eightfold-coordinated Pb atoms. On the basis of the structure determination, the empirically determined idealized formula follows a [8](Pb, As,Ag, Sn) [6](Sn,Fe)S3 stoichiometry. Crystalchemical arguments suggest Ag possibly to occupy interstitial sites according to the alternative formula [4](⃞,Ag) [8](Pb, As, Sn) [6](Sn,Fe) S3. The name of this new mineral species is in honor of R.J. Sureda Leston, head of the Department of Mineralogy and Economic Geology, University of Salta, Argentina.