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Joteite, Ca2CuAl[AsO4][AsO3(OH)]2(OH)2·5H2O, a new arsenate with a sheet structure and unconnected acid arsenate groups
- A. R. Kampf, S. J. Mills, R. M. Housley, G. R. Rossman, B. P. Nash, M. Dini, R. A. Jenkins
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- Journal:
- Mineralogical Magazine / Volume 77 / Issue 6 / August 2013
- Published online by Cambridge University Press:
- 05 July 2018, pp. 2811-2823
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Joteite (IMA2012-091), Ca2CuAl[AsO4][AsO3(OH)]2(OH)2·5H2O, is a new mineral from the Jote mine, Tierra Amarilla, Copiapó Province, Atacama, Chile. The mineral is a late-stage, low-temperature, secondary mineral occurring with conichalcite, mansfieldite, pharmacoalumite, pharmacosiderite and scorodite in narrow seams and vughs in the oxidized upper portion of a hydrothermal sulfide vein hosted by volcanoclastic rocks. Crystals occur as sky-blue to greenish-blue thin blades, flattened and twinned on {001}, up to ~300 μm in length, and exhibiting the forms {001}, {010}, {10}, {20} and {111}. The blades are commonly intergrown in wheat-sheaf-like bundles, less commonly in sprays, and sometimes aggregated as dense crusts and cavity linings. The mineral is transparent and has a very pale blue streak and vitreous lustre. The Mohs hardness is estimated at 2 to 3, the tenacity is brittle, and the fracture is curved. It has one perfect cleavage on {001}. The calculated density based on the empirical formula is 3.056 g/cm3. It is optically biaxial (–) with α = 1.634(1), β = 1.644(1), γ = 1.651(1) (white light), 2Vmeas = 78(2)° and 2Vcalc = 79.4°. The mineral exhibits weak dispersion, r < v. The optical orientation is X ≈ c*; Y ≈ b*. The pleochroism is Z (greenish blue) > Y (pale greenish blue) > X (colourless). The normalized electron-microprobe analyses (average of 5) provided: CaO 15.70, CuO 11.22, Al2O38.32, As2O546.62, H2O 18.14 (structure), total 100 wt.%. The empirical formula (based on 19 O a.p.f.u.) is: Ca1.98Cu1.00Al1.15As2.87H14.24O19. The mineral is slowly soluble in cold, concentrated HCl. Joteite is triclinic, P, with the cell parameters: a = 6.0530(2), b = 10.2329(3), c = 12.9112(4) Å, α = 87.572(2), β = 78.480(2), γ = 78.697(2)°, V = 768.40(4) Å3 and Z = 2. The eight strongest lines in the X-ray powder diffraction pattern are [dobs Å (I)(hkl)]: 12.76(100)(001), 5.009(23)(020), 4.206(26)(120,003,121), 3.92(24)(022,02,02), 3.40(25)(13), 3.233(19)(031,023,123,03), 2.97(132,201) and 2.91(15)(22,13). In the structure of joteite (R1 = 7.72% for 6003 Fo > 4σF), AsO4 and AsO3 (OH) tetrahedra, AlO6 octahedra and Cu2+O5 square pyramids share corners to form sheets parallel to {001}. In addition, 7- and 8-coordinate Ca polyhedra link to the periphery of the sheets yielding thick slabs. Between the slabs are unconnected AsO3(OH) tetrahedra, which link the slabs only via hydrogen bonding. The Raman spectrum shows features consistent with OH and/or H2O in multiple structural environments. The region between the slabs may host excess Al in place of some As.
Bluebellite and mojaveite, two new minerals from the central Mojave Desert, California, USA
- S. J. Mills, A. R. Kampf, A. G. Christy, R. M. Housley, G. R. Rossman, R. E. Reynolds, J. Marty
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- Journal:
- Mineralogical Magazine / Volume 78 / Issue 5 / October 2014
- Published online by Cambridge University Press:
- 05 July 2018, pp. 1325-1340
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Bluebellite, Cu6[I5+O3(OH)3](OH)7Cl and mojaveite, Cu6[Te6+O4(OH)2](OH)7Cl, are new secondary copper minerals from the Mojave Desert. The type locality for bluebellite is the D shaft, Blue Bell claims, near Baker, San Bernardino County, California, while cotype localities for mojaveite are the E pit at Blue Bell claims and also the Bird Nest drift, Otto Mountain, also near Baker. The two minerals are very similar in their properties. Bluebellite is associated particularly with murdochite, but also with calcite, fluorite, hemimorphite and rarely dioptase in a highly siliceous hornfels. It forms bright bluishgreen plates or flakes up to ~20 mm 620 mm 65 mm in size that are usually curved. The streak is pale bluish green and the lustre is adamantine, but often appears dull because of surface roughness. It is non-fluorescent. Bluebellite is very soft (Mohs hardness ~1), sectile, has perfect cleavage on {001} and an irregular fracture. The calculated density based on the empirical formula is 4.746 g cm–3. Bluebellite is uniaxial (–), with mean refractive index estimated as 1.96 from the Gladstone-Dale relationship. It is pleochroic O (bluish green) >> E (nearly colourless). Electron microprobe analyses gave the empirical formula Cu5.82I0.99Al0.02Si0.12O3.11(OH)9.80Cl1.09 based on 14 (O+Cl) a.p.f.u. The Raman spectrum shows strong iodate-related bands at 680, 611 and 254 cm–1. Bluebellite is trigonal, space group R3, with the unit-cell parameters: a = 8.3017(5), c = 13.259(1) Å , V = 791.4(1) Å 3 and Z = 3. The eight strongest lines in the powder X-ray diffraction (XRD) pattern are [dobs/Å (I) (hkl)]: 4.427(99)(003), 2.664(35)(211), 2.516(100)(21), 2.213(9)(006), 2.103(29)(033,214), 1.899(47)(312,21), 1.566(48)(140,217) and 1.479(29)(045,14,324).
Mojaveite occurs at the Blue Bell claims in direct association with cerussite, chlorargyrite, chrysocolla, hemimorphite, kettnerite, perite, quartz and wulfenite, while at the Bird Nest drift, it is associated with andradite, chrysocolla, cerussite, burckhardtite, galena, goethite, khinite, mcalpineite, thorneite, timroseite, paratimroseite, quartz and wulfenite. It has also been found at the Aga mine, Otto Mountain, with cerussite, chrysocolla, khinite, perite and quartz. Mojaveite occurs as irregular aggregates of greenish-blue plates flattened on {001} and often curved, which rarely show a hexagonal outline, and also occurs as compact balls, from sky blue to medium greenish blue in colour. Aggregates and balls are up to 0.5 mm in size. The streak of mojaveite is pale greenish blue, while the lustre may be adamantine, pearly or dull, and it is non-fluorescent. The Mohs hardness is ~1. It is sectile, with perfect cleavage on {001} and an irregular fracture. The calculated density is 4.886 g cm–3, based on the empirical formulae and unit-cell dimensions. Mojaveite is uniaxial (–), with mean refractive index estimated as 1.95 from the Gladstone-Dale relationship. It is pleochroic O (greenish blue) >> E (light greenish blue). The empirical formula for mojaveite, based on 14 (O+Cl) a.p.f.u., is Cu5.92Te1.00Pb0.08Bi0.01O4(OH)8.94Cl1.06. The most intense Raman bands occur at 694, 654 (poorly resolved), 624, 611 and 254 cm–1. Mojaveite is trigonal, space group R3, with the unit-cell parameters: a = 8.316(2), c = 13.202(6) Å and V = 790.7(1) Å 3. The eight strongest lines in the powder XRD pattern are [dobs/Å (I) (hkl)]: 4.403(91)(003), 2.672(28)(211), 2.512(100)(21), 2.110(27)(033,214), 1.889(34)(312,21,22), 1.570(39)(404,140,217), 1.481(34)(045,14,324) and 1.338(14)(422). Diffraction data could not be refined, but stoichiometries and unit-cell parameters imply that bluebellite and mojaveite are very similar in crystal structure. Structure models that satisfy bondvalence requirements are presented that are based on stackings of brucite-like Cu6MX14 layers, where M = (I or Te) and X = (O, OH and Cl). Bluebellite and mojaveite provide a rare instance of isotypy between an iodate containing I5+ with a stereoactive lone electron pair and a tellurate containing Te6+ with no lone pair.
Camaronesite, [Fe3+(H2O)2(PO3OH)]2(SO4)·1–2H2O, a new phosphate-sulfate from the Camarones Valley, Chile, structurally related to taranakite
- A. R. Kampf, S. J. Mills, B. P. Nash, R. M. Housley, G. R. Rossman, M. Dini
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- Journal:
- Mineralogical Magazine / Volume 77 / Issue 4 / June 2013
- Published online by Cambridge University Press:
- 05 July 2018, pp. 453-465
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Camaronesite (IMA 2012-094), [Fe3+(H2O)2(PO3OH)]2(SO4)·1–2H2O, is a new mineral from near the village of Cuya in the Camarones Valley, Arica Province, Chile. The mineral is a low-temperature, secondary mineral occurring in a sulfate assemblage with anhydrite, botryogen, chalcanthite, copiapite, halotrichite, hexahydrite, hydroniumjarosite, pyrite, römerite, rozenite and szomolnokite. Lavender-coloured crystals up to several mm across form dense intergrowths. More rarely crystals occur as drusy aggregates of tablets up to 0.5 mm in diameter and 0.02 mm thick. Tablets are flattened on {001} and exhibit the forms {001}, {104}, {015} and {018}. The mineral is transparent with white streak and vitreous lustre. The Mohs hardness is 2½, the tenacity is brittle and the fracture is irregular, conchoidal and stepped. Camaronesite has one perfect cleavage on {001}. The measured and calculated densities are 2.43(1) and 2.383 g/cm3, respectively. The mineral is optically uniaxial (+) with ω = 1.612(1) and ε = 1.621(1) (white light). The pleochroism is O (pale lavender) > E (colourless). Electron-microprobe analyses provided Fe2O331.84, P2O529.22, SO315.74, H2O 23.94 (based on O analyses), total 100.74 wt.%. The empirical formula (based on 2 P a.p.f.u.) is: Fe1.94(PO3OH)2(S0.96O4)(H2O)4·1.46H2O. The mineral is slowly soluble in concentrated HCl and extremely slowly soluble in concentrated H2SO4. Camaronesite is trigonal, R32, with cell parameters:a = 9.0833(5), c = 42.944(3) Å, V = 3068.5(3) Å3 and Z = 9. The eight strongest lines in the X-ray powder diffraction pattern are [dobs Å (I)(hkl)]: 7.74(45)(101), 7.415(100)(012), 4.545(72)(110), 4.426(26)(018), 3.862(32)(021,202,116), 3.298(93)(027,119), 3.179(25)(208) and 2.818(25)(1·1·12,125). In the structure of camaronesite (R1 = 2.28% for 1138 Fo > 4σF), three types of Fe octahedra are linked by corner sharing with (PO3OH) tetrahedra to form polyhedral layers perpendicular to c with composition [Fe3+(H2O)2(PO3OH)]. Two such layers are joined through SO4 tetrahedra (in two half-occupied orientations) to form thick slabs of composition [Fe3+(H2O)2(PO3OH)]2(SO4). Between the slabs are partially occupied H2O groups. The only linkages between the slabs are hydrogen bonds. The most distinctive component in the structure consists of two Fe octahedra linked to one another by three PO4 tetrahedra yielding an [Fe2(PO4)3] unit. This unit is also the key component in the sodium super-ionic conductor (NASICON) structure and has been referred to as the lantern unit. The polyhedral layers in the structure of camaronesite are similar to those in the structure of taranakite. The Raman spectrum exhibits peaks consistent with sulfate, phosphate, water and OH groups.
The dumortierite supergroup. II. Three new minerals from the Szklary pegmatite, SW Poland: Nioboholtite, (Nb0.6□0.4)Al6BSi3O18, titanoholtite, (Ti0.75□0.25)Al6BSi3O18, and szklaryite, □Al6BAs3+3O15
- A. Pieczka, R. J. Evans, E. S. Grew, L. A. Groat, C. Ma, G. R. Rossman
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- Journal:
- Mineralogical Magazine / Volume 77 / Issue 6 / August 2013
- Published online by Cambridge University Press:
- 05 July 2018, pp. 2841-2856
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Three new minerals in the dumortierite supergroup were discovered in the Szklary pegmatite, Lower Silesia, Poland. Nioboholtite, endmember (Nb0.6☐0.4)Al6B3Si3O18, and titanoholtite, endmember (Ti0.75☐0.25)Al6B3Si3O18, are new members of the holtite group, whereas szklaryite, endmember ☐Al6BAs3+3O15, is the first representative of a potential new group. Nioboholtite occurs mostly as overgrowths not exceeding 10 μm in thickness on cores of holtite. Titanoholtite forms patches up to 10 μm across in the holtite cores and streaks up to 5 μm wide along boundaries between holtite cores and the nioboholtite rims. Szklaryite is found as a patch ∼2 μm in size in As- and Sb- bearing dumortierite enclosed in quartz. Titanoholtite crystallized almost simultaneously with holtite and other Ta-dominant minerals such as tantalite-(Mn) and stibiotantalite and before nioboholtite, which crystallized simultaneously with stibiocolumbite during decreasing Ta activity in the pegmatite melt. Szklaryite crystallized after nioboholtite during the final stage of the Szklary pegmatite formation. Optical properties could be obtained only from nioboholtite, which is creamy-white to brownish yellow or grey-yellow in hand specimen, translucent, with a white streak, biaxial (–), nα = 1.740 – 1.747, nβ ∼ 1.76, nγ ∼ 1.76, and Δ < 0.020. Electron microprobe analyses of nioboholtite, titanoholtite and szklaryite give, respectively, in wt.%: P2O5 0.26, 0.01, 0.68; Nb2O5 5.21, 0.67, 0.17; Ta2O5 0.66, 1.18, 0.00; SiO2 18.68, 21.92, 12.78; TiO2 0.11, 4.00, 0.30; B2O3 4.91, 4.64, 5.44; Al2O3 49.74, 50.02, 50.74; As2O3 5.92, 2.26, 16.02; Sb2O3 10.81, 11.48, 10.31; FeO 0.51, 0.13, 0.19; H2O (calc.) 0.05, –, –, Sum 96.86, 96.34, 97.07, corresponding on the basis of O = 18–As–Sb to {(Nb0.26Ta0.02☐0.18)(Al0.27Fe0.05Ti0.01)☐0.21}Σ1.00Al6B0.92{Si2.03P0.02(Sb0.48As0.39Al0.07}Σ3.00(O17.09OH0.04☐0.87)Σ18.00, {(Ti0.32 Nb0.03 Ta0.03☐0.10)(Al0.35 Ti0.01 Fe0.01)☐0.15 }Σ1.00 Al6 B0.86 {Si2 . 3 6 (Sb0.5 1 As0.14 )}Σ3.01(O17.35☐0.65)Σ18.00 and {☐0.53 (Al0.41 Ti0.02 Fe0.02 )(Nb0.01☐0.01 )}Σ1.00Al6 B1.01 {(As1.07 Sb0.47 Al0.03 ) Si1.37 P0.06 }Σ3.00(O16.46☐1.54 )Σ18.00. Electron backscattered diffraction indicates that the three minerals are presumably isostructural with dumortierite, that is, orthorhombic symmetry, space group Pnma (no. 62), and unit-cell parameters close to a = 4.7001, b = 11.828, c = 20.243 Å, with V = 1125.36 Å3 and Z = 4; micro-Raman spectroscopy provided further confirmation of the structural relationship for nioboholtite and titanoholtite. The calculated density is 3.72 g/cm3 for nioboholtite, 3.66 g/cm3 for titanoholtite and 3.71 g/cm3 for szklaryite. The strongest lines in X-ray powder diffraction patterns calculated from the cell parameters of dumortierite of Moore and Araki (1978) and the empirical formulae of nioboholtite, titanoholtite and szklaryite are [d, Å, I (hkl)]: 10.2125, 67, 46, 19 (011); 5.9140, 40, 47, 57 (020); 5.8610, 66, 78, 100 (013); 3.4582, 63, 63, 60 (122); 3.4439, 36, 36, 34 (104); 3.2305, 100, 100, 95 (123); 3.0675, 53, 53, 50 (105); 2.9305, 65, 59, 51 (026); 2.8945, 64, 65, 59 (132), respectively. The three minerals have been approved by the IMA CNMNC (IMA 2012-068, 069, 070) and were named for their relationship to holtite and occurrence in the Szklary pegmatite, respectively.
The dumortierite supergroup. I. A new nomenclature for the dumortierite and holtite groups
- A. Pieczka, R. J. Evans, E. S. Grew, L. A. Groat, C. Ma, G. R. Rossman
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- Journal:
- Mineralogical Magazine / Volume 77 / Issue 6 / August 2013
- Published online by Cambridge University Press:
- 05 July 2018, pp. 2825-2839
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Although the distinction between magnesiodumortieite and dumortierite, i.e. Mg vs. Al dominance at the partially vacant octahedral Al1 site, had met current criteria of the IMA Commission on New Minerals, Nomenclature and Classification (CNMNC) for distinguishing mineral species, the distinction between holtite and dumortierite had not, since Al and Si are dominant over Ta and (Sb, As) at the Al1 and two Si sites, respectively, in both minerals. Recent studies have revealed extensive solid solution between Al, Ti, Ta and Nb at Al1 and between Si, As and Sb at the two Si sites or nearly coincident (As, Sb) sites in dumortierite and holtite, further blurring the distinction between the two minerals.
This situation necessitated revision in the nomenclature of the dumortierite group. The newly constituted dumortierite supergroup, space group Pnma (no. 62), comprises two groups and six minerals, one of which is the first member of a potential third group, all isostructural with dumortierite. The supergroup, which has been approved by the CNMNC, is based on more specific end-member compositions for dumortierite and holtite, in which occupancy of the Al1 site is critical.
(1) Dumortierite group, with Al1 = Al3+, Mg2+ and ☐, where ☐ denotes cation vacancy. Charge balance is provided by OH substitution for O at the O2, O7 and O10 sites. In addition to dumortierite, endmember composition AlAl6BSi3O18, and magnesiodumortierite, endmember composition MgAl6BSi3O17(OH), plus three endmembers, “hydroxydumortierite”, ☐Al6BSi3O15(OH)3 and two Mg-Ti analogues of dumortierite, (Mg0.5Ti0.5)Al6BSi3O18 and (Mg0.5Ti0.5)Mg2Al4BSi3O16(OH)2, none of which correspond to mineral species. Three more hypothetical endmembers are derived by homovalent substitutions of Fe3+ for Al and Fe2+ for Mg.
(2) Holtite group, with Al1 = Ta5+, Nb5+, Ti4+ and ☐. In contrast to the dumortierite group, vacancies serve not only to balance the extra charge introduced by the incorporation of pentavalent and quadrivalent cations for trivalent cations at Al1, but also to reduce repulsion between the highly charged cations. This group includes holtite, endmember composition (Ta0.6☐0.4)Al6BSi3O18, nioboholite (2012-68), endmember composition (Nb0.6☐0.4)Al6BSi3O18, and titanoholtite (2012-69), endmember composition (Ti0.75☐0.25)Al6BSi3O18.
(3) Szklaryite (2012-70) with Al1 = ☐ and an endmember formula ☐Al6BAs3+3O15. Vacancies at Al1 are caused by loss of O at O2 and O7, which coordinate the Al1 with the Si sites, due to replacement of Si4+ by As3+ and Sb3+, and thus this mineral does not belong in either the dumortierite or the holtite group. Although szklaryite is distinguished by the mechanism introducing vacancies at the Al1 site, the primary criterion for identifying it is based on occupancy of the Si/As, Sb sites: (As3+ + Sb3+) > Si4+ consistent with the dominant-valency rule. A Sb3+ analogue to szklaryite is possible.
Microanalysis of Hafnian Zircon
- C Ma, G R Rossman
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- Journal:
- Microscopy and Microanalysis / Volume 11 / Issue S02 / August 2005
- Published online by Cambridge University Press:
- 01 August 2005, pp. 1304-1305
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- August 2005
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Extended abstract of a paper presented at Microscopy and Microanalysis 2005 in Honolulu, Hawaii, USA, July 31--August 4, 2005
Mineral Dielectric Constants and the Oxide Additivity Rule
- R. D. Shannon, M. A. Subramanian, A. N. Marian, G. R. Rossman
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- MRS Online Proceedings Library Archive / Volume 150 / 1989
- Published online by Cambridge University Press:
- 21 February 2011, 197
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- 1989
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The 1 Miz dielectric constants of a variety of synthetic aluminate garnets: Y3Al5O12, Ho3A15O12, Y2.93Nd.07Sc2Al3O12 and Gd2.95Nd.05Sc1 98Cr .02A13O12 and several silicates: CaB2Si2O8 (danburite), Ca3Al2Si3O12 (grossular) and Mg2Al4Si5O18(cordierite) were determined using the two-terminal method with edge corrections. These data and polarizabilities derived from the published single crystal dielectric constants of simple oxides were used to compare compound polarizabilities obtained from the Clausius-Mosotti equation and the oxide additivity rule.