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Angastonite, CaMgAl2(PO4)2(OH)4·7H2O: a new phosphate mineral from Angaston, South Australia
- S. J. Mills, L. A. Groat, S. A. Wilson, W. D. Birch, P. S. Whitfield, M. Raudsepp
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- Journal:
- Mineralogical Magazine / Volume 72 / Issue 5 / October 2008
- Published online by Cambridge University Press:
- 05 July 2018, pp. 1011-1020
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Angastonite, ideally CaMgAl2(PO4)2(OH)4-7H2O, is a newly defined mineral from the Penrice marble quarry, South Australia. The mineral occurs as snow-white crusts and coatings up to ∼1 mm thick associated with minyulite, perhamite, crandallite and apatite-(CaF). The streak is white, the lustre is pearly and the estimated hardness is 2 on the Mohs scale. Angastonite forms platy crystals with the forms {010} (prominent), {101}, {101} and {100} (rare), and also occurs as replacements of an unknown pre-existing mineral. There is one cleavage direction on ﹛010} and no twinning has been observed. Angastonite is triclinic, P1̄, with a = 13.303(1) Å, b = 27.020(2) Å, c = 6.1070(7) Å α = 89.64(1)°, β = 83.44(1)°, γ = 80.444(8)°, V = 2150.5(4) Å3, with Z = 6. The mineral is optically biaxial (+), with refractive indices of α = 1.566(2), β = 1.572(2) and γ 1.584(2) and with 2Vmeas = 70(2)° and 2Vcalc = 71°. Orientation: X ≈ a, Y ≈ b, Z ≈ c; with crystals showing parallel extinction and no axial dispersion. Dmeas is 2.47 g/cm3, whilst Dcalc is 2.332 g/cm3. The strongest four powder-diffraction lines [d in Å, (I/I°), hkl] are: 13.38, (100), 020; 11.05, (25), 11̄0; 5.73, (23), 101, 230 and 111; 8.01, (21), 130. Angastonite is likely to be related to the montgomeryite-group members and have a similar crystal structure, based on slabs of phosphate tetrahedra and Al octahedra.
The crystal chemistry of holtite
- L. A. Groat, E. S. Grew, R. J. Evans, A. Pieczka, T. S. Ercit
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- Journal:
- Mineralogical Magazine / Volume 73 / Issue 6 / December 2009
- Published online by Cambridge University Press:
- 05 July 2018, pp. 1033-1050
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Holtite, approximately (Al,Ta,□)Al6(BO3)(Si,Sb3+,As3+)Σ3O12(O,OH,□s)Σ3, is a member of the dumortierite group that has been found in pegmatite, or alluvial deposits derived from pegmatite, at three localities: Greenbushes, Western Australia; Voron'i Tundry, Kola Peninsula, Russia; and Szklary. Lower Silesia, Poland. Holtite can contain >30 wt.% Sb2O3, As2O3, Ta2O5, Nb2O5, and TiO2 (taken together), but none of these constituents is dominant at a crystallographic site, which raises the question whether this mineral is distinct from dumortierite. The crystal structures of four samples from the three localities have been refined to R1 = 0.02—0.05. The results show dominantly: Al, Ta, and vacancies at the Al(l) position; Al and vacancies at the Al(2), (3) and (4) sites; Si and vacancies at the Si positions; and Sb, As and vacancies at the Sb sites for both Sb-poor (holtite I) and Sb-rich (holtite II) specimens. Although charge-balance calculations based on our single-crystal structure refinements suggest that essentially no water is present, Fourier transform infrared spectra confirm that some OH is present in the three samples that could be measured. By analogy with dumortierite, the largest peak at 3505-3490 cm-1 is identified with OH at the O(2) and O(7) positions. The single-crystal X-ray refinements and FTIR results suggest the following general formula for holtite: Al7-[5x+y+z]/3 (Ta,Nb)x□[2x+y+z]\3,BSi3-y(Sb,As)yO18-y-z(OH)z, where x is the total number of pentavalent cations, y is the total amount of Sb + As, and z ⩽ y is the total amount of OH. Comparison with the electron microprobe compositions suggests the following approximate general formulae Al5.83(Ta,Nb)0.50□0.67BSi2.50(Sb,As)0.50O17.00(OH)0.50 and Al5.92(Ta,Nb)0.25□0.83BSi2.00(Sb,As)1.00O16.00(OH)1.00 for holtite I and holtite II respectively. However, the crystal structure refinements do not indicate a fundamental difference in cation ordering that might serve as a criterion for recognizing the two holtites as distinct species, and anion compositions are also not sufficiently different. Moreover, available analyses suggest the possibility of a continuum in the Si/(Sb + As) ratio between holtite I and dumortierite, and at least a partial continuum between holtite I and holtite II. We recommend that use of the terms holtite I and holtite II be discontinued.
The crystal structure and chemical composition of cumengéite
- F. C. Hawthorne, L. A. Groat
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- Journal:
- Mineralogical Magazine / Volume 50 / Issue 355 / March 1986
- Published online by Cambridge University Press:
- 05 July 2018, pp. 157-162
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The crystal structure of cumengéite, Pb21Cu20Cl42(OH)40, tetragonal, a= 15.065(2), c= 24.436(5) Å, V = 5546(2) Å3, space group I4/mmm, Z = 2, has been solved by direct methods and refined by least-squares to an R index of 7.1 % for 1158 observed (I > 2.5σ I) reflections. The cumengéite structure shows a very diverse range of cation coordinations. There are five distinct Pb sites with the following coordination polyhedra: octahedron, square antiprism, augmented trigonal prism, a very distorted biaugmented trigonal prism and a fairly regular biaugmented trigonal prism, the latter being only half-occupied; there are two distinct Cu sites with octahedral and square pyramidal coordination respectively. The coordination polyhedra share elements to form prominent columns or rods of polyhedra parallel to the c-axis and centred on the 4-fold axes of the unit cell. These rods form a body-centred array, and link by sharing elements of their coordination polyhedra.
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.
Holtite and dumortierite from the Szklary Pegmatite, Lower Silesia, Poland
- A. Pieczka, E. S. Grew, L. A. Groat, R. J. Evans
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- Journal:
- Mineralogical Magazine / Volume 75 / Issue 2 / April 2011
- Published online by Cambridge University Press:
- 05 July 2018, pp. 303-315
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The Szklary holtite is represented by three compositional varieties: (1) Ta-bearing (up to 14.66 wt.% Ta2O5), which forms homogeneous crystals and cores within zoned crystals; (2) Ti-bearing (up to 3.82 wt.% TiO2), found as small domains within the core; and (3) Nb-bearing (up to 5.30 wt.% Nb2O5,) forming the rims of zoned crystals. All three varieties show variable Sb+As content, reaching 19.18 wt.% Sb2O3 (0.87 Sb a.p.f.u.) and 3.30 wt.% As2O3 (0.22 As a.p.f.u.) in zoned Ta-bearing holtite, which constitutes the largest Sb+As content reported for the mineral. The zoning in holtite is a result of Ta-Nb fractionation in the parental pegmatite-forming melt together with contamination of the relatively thin Szklary dyke by Fe, Mg and Ti. Holtite and the As- and Sb-bearing dumortierite, which in places overgrows the youngest Nb-bearing zone, suggest the following crystallization sequence: Ta-bearing holtite → Ti-bearing holtite → Nb-bearing holtite → As- and Sb-bearing, (Ta,Nb,Ti)-poor dumortierite → As- and Sb-dominant, (Ta,Nb,Ti)-free dumortierite-like mineral (16.81 wt.% As2O3 and 10.23 wt.% Sb2O3) with (As+Sb) > Si. The last phase is potentially a new mineral species. Al6□☐(Sb,As)3O15, or Al5☐2B(Sb,As)3O12(OH)3, belonging to the dumortierite group. The Szklary holtite shows no evidence of clustering of compositions around ‘holtite I’ and ‘holtite II'. Instead, the substitutions of Si4+ by Sb3++As3+ at the Si/Sb sites and of Ta5+ by Nb5+ or Ti4+ at the Al(l) site suggest possible solid solutions between: (1) (Sb,As)-poor and (Sb,As)-rich holtite; (2) dumortierite and the unnamed (As+Sb)-dominant dumortierite-like mineral; and (3) Ti-bearing dumortierite and holtite. i.e. our data provide further evidence for miscibility between holtite and dumortierite, but leave open the question of defining the distinction between them. The Szklary holtite crystallized from the melt along with other primary Ta-Nb-(Ti) minerals such as columbite-(Mn), tantalite-(Mn), stibiotantalite and stibiocolumbite as the availability of Ta decreased. The origin of the parental melt can be related to anatexis in the adjacent Sowie Mountains complex, leading to widespread migmatization and metamorphic segregation in pelitic-psammitic sediments metamorphosed at ∼390—380 Ma.
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.