Alessandro Guastoni

Chemical and paragenetic data on gadolinite-group minerals from Baveno and Cuasso al Monte, southern Alps, Italy

Abstract The crystal structure of a rubidian cesian phlogopite-1M from pegmatite exocontacts at Red Cross Lake, Manitoba, monoclinic, a = 5.343(1),6 = 9.247(2),c = 10.397(3) Å, β = 100.04(2)°, V= 505.8(2) Å3, has been refined to an R index of 4.5% based on 519 observed reflections measured with graphite-monochromated MoΚα X-radiation on an automated four-circle diffractometer. The crystal used in the collection of the X-ray intensity data was also analyzed by electron microprobe, giving the unit formula (K0.46Rb0.28Cs0.23)(Mg1.20Fe1.00Al0.38Li0.34Mn0.04Ti0.04)(Si2.91Al1.09)O10[(OH)1.55F0.45]. The interlayer site, X, contains large amounts of Rb and Cs, and cell dimensions and the distance are in accord with data from synthetic Rb and Cs phlogopites and plutonic phlogopites. The interlayer coordination is much more regular in rubidian cesian phologopite than in other trioctahedral micas, defining a trend of increasing regularity with increasing interlayer-cation size.

On the crystal structure and crystal chemistry of pollucite, (Cs,Na)16Al16Si32O96·nH2O: A natural microporous material of interest in nuclear technology

Abstract The crystal structure and crystal chemistry of two natural pollucite samples, from Buckfield, Oxford County, Maine (sample M3), and from Kanzit Mawaie, Laghman, Nooristan, Afghanistan (sample N5), have been investigated by means of wavelength-dispersive X-ray microanalysis, thermogravimetric analysis, single-crystal X-ray and neutron diffraction, and single-crystal Fourier-transform infrared spectroscopy. The X-ray and neutron diffraction patterns of the two pollucite crystals show a metrically cubic unit cell [with aM3 = 13.6914(6) Å and aN5 = 13.6808(6) Å by neutron diffraction data; the deviation from isometry is <1.5σ(li), where li is the unrestrained unit-cell length] and the reflection conditions are consistent with the space group Ia3d. Anisotropic neutron structural refinements gave final agreement indices: R1 = 0.0543 for 32 refined parameters and 372 unique reflections with Fo > 4σ(Fo) for M3 and R1 = 0.0693 for 31 refined parameters and 331 unique reflections with Fo > 4σ(Fo) for N5. The structure refinements show a disordered Si/Al-distribution in the tetrahedral framework. The analysis of the difference-Fourier maps of the nuclear density confirms the presence of extraframework water molecules with oxygen sharing the Cs site (at 1/8, 1/8, 1/8, Wyckoff-16b position). However, the minima, ascribable to the proton sites, are very weak in density. Two possible proton positions, leading to a reasonable H2O configuration, are given, and the possible hydrogen bonding is described. Sodium is located at 1/4, 1/8, 0 (Wyckoff-24c position). The main IR absorption bands in the regions typical of H2O are assigned, and the presence of hydroxyls in the studied samples is ruled out. Neutron diffraction and FTIR data agree with the presence of very weak hydrogen bonds in the structure. The detailed description of the crystal structure and crystal chemistry of pollucite (e.g., Si/Al-distribution, configuration of the extra-framework content, possible hydrogen bonding scheme) reported in this study is the key to understand the high thermo-elastic stability of pollucite, the immobility of Cs at non-ambient conditions, and the extremely low leaching rate of Cs, which make this open-framework silicate a promising material with potential use for fixation and deposition of Cs radioisotopes

Mineral chemistry and alteration of rare earth element (REE) carbonates from alkaline pegmatites of Mount Malosa, Malawi

Abstract In this study, the mineral chemistry and alteration of bastnäsite-(Ce), parisite-(Ce), and synchysite- (Ce) was investigated by EMPA, TG, DTG, CHNS, and SCXRD techniques. Relevant chemical data on light and volatile elements and X-ray diffraction data useful to evaluate the effect of OH content on the unit-cell volume of such carbonates are provided. Significant amounts of OH in both the parisite-(Ce) and synchysite-(Ce) were found, and these data are the first direct evidence of hydration for these carbonates. Single-crystal X-ray diffraction data showed that hydration causes an increase in the unit-cell volume for parisite and synchysite. Parisite-(Ce) and synchysite-(Ce) OH end-members have not been described in nature so far, and the amount of water must be taken into account for evaluating changes in stability field conditions. Textural relationships and replacement processes are discussed.

Dalnegroite, Tl5-xPb2x(As,Sb)21xS34, a new thallium sulphosalt from Lengenbach quarry, Binntal, Switzerland

Abstract Dalnegroite, ideally Tl4Pb2(As12Sb8)Σ20S34, is a new mineral from Lengenbach, Binntal, Switzerland. It occurs as anhedral to subhedral grains up to 200 μm across, closely associated with realgar, pyrite, Sb-rich seligmanite in a gangue of dolomite. Dalnegroite is opaque with a submetallic lustre and shows a brownish-red streak. It is brittle; the Vickers hardness (VHN25) is 87 kg mm-2 (range: 69-101) (Mohs hardness ~3-3½). In reflected light, dalnegroite is highly bireflectant and weakly pleochroic, from white to a slightly greenish-grey. In cross-polarized light, it is highly anisotropic with bluish to green rotation tints and red internal reflections. According to chemical and X-ray diffraction data, dalnegroite appears to be isotypic with chabournéite, Tl5-xPb2x(Sb,As)21-xS34. It is triclinic, probable space group P1, with a = 16.217(7) Å, b = 42.544(9) Å, c = 8.557(4) Å, α = 95.72(4)°, β = 90.25(4)°, γ = 96.78(4)°, V = 5832(4) Å3, Z = 4. The nine strongest powder-diffraction lines [d (Å) (I/I0) (hkl)] are: 3.927 (100) (2̅10 0); 3.775 (45) (22̅2); 3.685 (45) (4̅60); 3.620 (50) (440); 3.124 (50) (2̅8̅2); 2.929 (60) (42̅2); 2.850 (70) (4̅42); 2.579 (45) (0 1̅4̅ 2); 2.097 (60) (024). The mean of 11 electron microprobe analyses gave elemental concentrations as follows: Pb 10.09(1) wt.%, Tl 20.36(1), Sb 23.95(1), As 21.33(8), S 26.16(8), totalling 101.95 wt.%, corresponding to Tl4.15Pb2.03(As11.86Sb8.20)S34. The new mineral is named for Alberto Dal Negro, Professor in Mineralogy and Crystallography at the University of Padova since 1976.

New insights into the crystal chemistry of epididymite and eudidymite from Malosa, Malawi: A single-crystal neutron diffraction study

Abstract The crystal chemistry of two dimorphic hydrated sodium beryllium silicates, epididymite [a = 12.7334(4), b = 13.6298(5), c = 7.3467(3) Å, V = 1275.04 Å3, space group Pnma)] and eudidymite [a = 12.6188(10), b = 7.3781(5), c = 13.9940(9) Å, β = 103.762(5)°, V = 1265.47 Å3, space group C2/c] from Malosa, Malawi, has been reinvestigated by means of energy dispersive X-ray spectroscopy, thermo-gravimetric analysis, inductively coupled plasma-optical emission spectroscopy and single-crystal neutron diffraction. Two anisotropic structure refinements have been performed with final agreement index R1 = 0.0317 for 137 refined parameters and 2261 unique reflections with Fo > 4σ(Fo) for epididymite, and R1 = 0.0478 for 136 refined parameters and 1732 unique reflections with Fo > 4σ(Fo) for eudidymite. The analysis of the difference-Fourier maps of the nuclear density of the two dimorphs confirms the presence of extra-framework water molecules in both, and not hydroxyl groups as wrongly reported in previous studies and in several crystal-structure databases. The correct chemical formula of edipidymite and eudidymite is Na2Be2Si6O15·H2O (Z = 4). The configuration of the water molecules and the hydrogen bonds are fully described for both the dimorphs. The chemical analyses show that a small, but significant, amount of Al and Fe (most likely substituting for Si in the tetrahedral sites) and K (substituting for Na as an extra-framework cation) occurs in both dimorphs

Mn-rich graftonite, ferrisicklerite, staněkite and Mn-rich vivianite in a granitic pegmatite at Soè Valley, central Alps, Italy

Abstract Mn-rich graftonite, (Ca,Mn2+)(Fe2+,Mn2+)2(PO4)2, ferrisicklerite, Li1-x(Fe3+,Mn2+)PO4, manganoan apatite, (Ca,Mn2+,Fe2+Mg)(PO4)3Cl, stanĕkite, Fe3+Mn2+O(PO4) and Mn-rich vivianite, (Fe2+)3(PO4)2‧8H2O, occurring in a granitic pegmatite at Soè Valley (central Alps, Italy) were characterized by powder and single-crystal X-ray diffraction (XRD) and electron microprobe analyses. Geochemically, the Mn-rich graftonite phases are poorly evolved Fe/Mn-phosphates of rare-earth elements-lithium (REE-Li) granitic pegmatites. The assemblage Mn-rich graftonite + ferrisicklerite + stanĕkite has rarely been documented in pegmatites. In the Soè Valley pegmatite, ferrisicklerite forms exsolution lamellae with Mn-rich graftonite associated with manganoan apatite and stanĕkite. Graftonite is associated with Mn-rich vivianite. Powder and single-crystal XRD data indicate that the unit-cell volume of graftonite increases as a function of Mn2+ content. Stanĕkite shows a distinctly smaller unit-cell volume with respect to previously reported stanĕkites, probably due to reduced Mn2+. Vivianite with significant Mn2+ has a unit-cell volume similar to nearly Mn-free vivianite. The formation of Mn-rich graftonite and manganoan apatite is related to destabilization of Mn-rich almandine and biotite during pegmatite formation. Ferrisicklerite forms exsolution lamellae along the 010 cleavage planes of Mn-rich graftonite, whereas stanĕkite forms by alteration of ferrisicklerite and Mn-rich vivianite due to circulation of late-stage hydrothermal fluids.

Scandium silicates from the Baveno and Cuasso al Monte NYF-granites, Southern Alps (Italy) : Mineralogy and genetic inferences

Abstract A chemical and paragenetic study has been performed on Sc silicates and Sc-bearing beryl occurring in Hercynian NYF-miarolitic pink granite and granophyric leucogranite at Baveno and Cuasso al Monte, Western Southern-Alps, Italy. In the Baveno and Cuasso al Monte plutons, detailed field work allowed the discovery of a significant number of crystals of bazzite, thortveitite, scandiobabingtonite, cascandite, and jervisite representative of all the known morphological and color varieties of these minerals in the two localities. Other studied samples belong to the historic collections of the Natural History Museum of Milan. Except for beryl, which crystallizes relatively early in aplitic granophyre, all the other Sc minerals crystallize as late-stage phases in cavities associated with fluorite. Chemical analyses reveal moderate Sc enrichment at the rim of beryl crystals. Bazzite displays a relatively large chemical variation, from .primitive. compositions enriched in Fe2O3 and Al2O3, to .highly evolved. compositions with values of Sc2O3 up to 17.54 wt%. Scandiobabingtonite shows a perfect inverse correlation between Fe3+ and Sc concentrations, suggesting complete solid solution between babingtonite and its Sc analogues. A wide variety of compositions have been determined for cascandite, significantly extending the compositional range of this mineral. In particular, the MnO content ranges from 0.37 to 4.87 wt%. The jervisite crystals analyzed in this work have rather homogeneous compositions much closer to the end-member if compared with the holotype analysis reported in literature. Thortveitite shows a wide range of compositions with variation in Sc2O3, Y2O3, HREE, and Fe2O3. Significant Fluctuations of the Sc/Yb ratios are in agreement with similar complex variations in the ratios between REE (e.g., Y/Dy) reported in the literature for crystals of gadolinite-group minerals from the same localities. Two different genetic models are discussed to explain the precipitation of Sc silicates as late stage phases in cavities. (1) during the latest stages of magma crystallization, HFSE and Sc were extracted from the silicate liquid and partitioned into fluids due to the complexing effect of F. Indeed, in view of the NYF geochemistry of the granite and the significant abundance of the associated F-bearing minerals, Fluorides (but not other complexing agents such as carbonates and phosphates) played the major role in concentrating HFSE and Sc. In cavities, such elements resulted in a series of rare accessory phases when F was extracted from Fluids because of the precipitation of zinnwaldite and Fluorite. (2) HFSE, Sc, and Y+REE were mainly incorporated by gadolinite-(Y) and siderophyllite crystallizing from residual magma. Many of the accessory phases crystallized in cavities because of the aggressive effect of subcritical hydrous, F-rich Fluids on the previously formed gadolinite-(Y) (liberating REE, Y, B, Be, Fe, Ca), siderophyllite (liberating Fe, Ti, and possibly Nb-Ta, Sc, etc.), and feldspars (liberating Ca, P, Cs, Ba). This second model is consistent with the widespread hydrothermal alteration of the Baveno and Cuasso al Monte granites and granophyres

Tl-bearing sulfosalt from the Lengenbach quarry, Binn Valley, Switzerland: Philrothite, TlAs3S5

Abstract Philrothite, ideally TlAs3S5, is a new mineral from the Lengenbach quarry in the Binn Valley, Valais, Switzerland. It occurs as very rare crystals up to 200 mm across on realgar associated with smithite, rutile and sartorite. Philrothite is opaque with a metallic lustre and shows a dark brown streak. It is brittle; the Vickers hardness (VHN25) is 128 kg/mm2 (range: 120-137) (Mohs hardness of 3-3½). In reflected light philrothite is moderately bireflectant and weakly pleochroic from dark grey to light grey. Under crossed polars it is anisotropic with grey to bluish rotation tints. Internal reflections are absent. Reflectance percentages for the four COM wavelengths (Rmin and Rmax) are: 26.5, 28.8 (471.1 nm), 25.4, 27.2 (548.3 nm), 24.6, 26.3 (586.6 nm) and 24.0, 25.1 (652.3 nm), respectively. Philrothite is monoclinic, space group P21/c, with a = 8.013(2), b = 24.829(4), c = 11.762(3) Å , b = 132.84(2)°, V = 1715.9(7) Å3, Z = 8. It represents the N = 4 homologue of the sartorite homologous series. In the crystal structure [R1 = 0.098 for 1217 reflections with I > 2σ(I)], Tl assumes tricapped prismatic sites alternating to form columns perpendicular to the b axis. Between the zigzag walls of Tl coordination prisms, coordination pyramids of As(Sb) form diagonally-oriented double layers separated by broader interspaces which house the lone electron pairs of these elements. The eight strongest calculated powder-diffraction lines [d in Å (I/I0) (hkl)] are: 12.4145 (52) (020); 3.6768 (100) (1̄61); 3.4535 (45) (131); 3.0150 (46) (1̄53); 2.8941 (52) (1̄81); 2.7685 (76) (230); 2.7642 (77) (2̄34); 2.3239 (52) (092). A mean of five electron microprobe analyses gave Tl 26.28(12), Pb 6.69(8), Ag 2.50(4), Cu 0.04(2), Hg 0.07(2), As 32.50(13), Sb 3.15(3), S 26.35(10), total 97.58 wt.%, corresponding, on the basis of a total of nine atoms, to (Tl0.789Pb0.198)∑=0.987 (As2.662Sb0.159Ag0.142Cu0.004Hg0.002)∑=2.969S5.044. The new mineral has been approved by the Commission on New Minerals, Nomenclature and Classification (CNMNC) of the International Mineralogical Association (2013-066) and named for Philippe Roth (b. 1963), geophysicist and well known mineral expert on the Lengenbach minerals for more than 25 years.

The crystal structure of dalnegroite, Tl5–xPb2x(As,Sb)21–xS34: a masterpiece of structural complexity

Abstract The crystal structure of the rare mineral dalnegroite, Tl5−xPb2x(As,Sb)21−xS34 with x ≈ 1, was determined for a crystal from Lengenbach, Binn Valley, Switzerland. The structure is triclinic, space group P1, with a = 16.218(3), b = 42.546(7), c = 8.558(1) Å, α = 95.70(4), β = 90.18(3), γ = 96.38(4)º, V = 5838.9(9) Å3, Z = 4. Refinement of an isotropic model led to an R1 index of 0.0536 for 22226 observed reflections and 980 parameters, and R1 = 0.0590 for all 25266 independent reflections. Although dalnegroite cannot be considered a layered compound, its structure can be usefully described as a regular alternation of two kinds of layers stacked along the b axis, with four layers in the unit cell: (1) a layer 7.8 Å thick, at y ≈ 0.15 and 0.65, can be considered as derived from the SnS archetype; (2) a layer 13.6 Å thick, at y ≈ 0.35 and 0.85, derived from the PbS archetype. Different chemical compositions, such as Tl:Pb and Sb:As ratios, for different samples belonging to the chabournéite-dalnegroite family could play a central role in controlling different degrees of order, leading to different superstructures.

Raberite, Tl5Ag4As6SbS15, a new Tl-bearing sulfosalt from Lengenbach quarry, Binn valley, Switzerland: description and crystal structure

Abstract Raberite, ideally Tl5Ag4As6SbS15, is a new mineral from Lengenbach quarry in the Binn Valley, Valais, Switzerland. It occurs very rarely as euhedral crystals up to 150 μm across associated with yellow needle-like smithite, realgar, hatchite and probable trechmannite, edenharterite, jentschite and two unidentified sulfosalts. Raberite is opaque with a metallic lustre and has a dark brown-red streak. It is brittle with a Vickers hardness (VHN10) of 52 kg mm-2 (range 50-55) corresponding to a Mohs hardness of 2½-3. In reflected light raberite is moderately bireflectant and very weakly pleochroic from light grey to a slightly greenish grey. It is very weakly anisotropic with greyish to light blue rotation tints between crossed polars. Internal reflections are absent. Reflectance percentages for the four COM wavelengths [listed as Rmin, Rmax, (λ)] are 30.6, 31.8 (471.1 nm), 28.1, 29.3 (548.3 nm), 27.1, 28.0 (586.6 nm), and 25.8, 26.9 (652.3 nm). Raberite is triclinic, space group P1̄, with a = 8.920(1), b = 9.429(1), c = 20.062(3) Å, α = 79.66(1), β = 88.84(1), γ = 62.72(1)º, V = 1471.6(4) Å3 and Z = 2. The crystal structure [R1 = 0.0827 for 2110 reflections with I > 2σ(I)] consists of columns of nine-coordinate Tl atoms forming irregular polyhedra extending along [001] and forming sheets parallel to (010). The columns are decorated by corner-sharing MS3 pyramids (M = As, Sb) and linked by AgS3 triangles. Of the seven M positions, one is dominated by Sb and the others by As; the mean M-S bond distances reflect As ↔ Sb substitution at these sites. The eight strongest lines in the powder diffraction pattern [dcalc in Å (I) (hkl)] are: 3.580 (100) (11̄3); 3.506 (58) (1̄2̄3); 3.281 (73) (006); 3.017 (54) (1̄23); 3.001 (98) (133); 2.657 (51) (226); 2.636 (46) (300); 2.591 (57) (330). A mean of 9 electron microprobe analyses gave Tl 39.55(13), Ag 18.42(8), Cu 0.06(2), As 17.08(7), Sb 5.61(6), S 19.15(11); total 99.87 wt.%, which corresponds to Tl4.85Ag4.28Cu0.02As5.72Sb1.16S14.97 with 31 atoms per formula unit. The new mineral has been approved by the IMA-CNMNC Commission (IMA 2012-017) and is named for Thomas Raber, an expert on Lengenbach minerals.