Cynthia K. W. Ma

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, □Al6B O15

Abstract Three new minerals in the dumortierite supergroup were discovered in the Szklary pegmatite, Lower Silesia, Poland. Nioboholtite, endmember (Nb0.6⃞0.4)Al6B3Si3O18, and titanoholtite, endmember (Ti0.75⃞0.25)Al6B3Si3O18, are new members of the holtite group, whereas szklaryite, endmember ⃞Al6BAs33+O15, 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 {(Nb0.26Ta0.02⃞0.18)(Al0.27Fe0.05Ti0.01)⃞0.21}∑1.00Al6B0.92{Si2.03P0.02(Sb0.48As0.39Al0.07}∑3.00(O17.09OH0.04⃞0.87)∑18.00, {(Ti0.32Nb0.03Ta0.03⃞0.10)(Al0.35Ti0.01Fe0.01)⃞0.15}∑1.00Al6B0.86{Si2.36(Sb0.51As0.14)}∑3.01(O17.35⃞0.65)∑18.00 and {⃞0.53(Al0.41Ti0.02Fe0.02)(Nb0.01⃞0.01)}∑1.00Al6B1.01{(As1.07Sb0.47Al0.03)Si1.37P0.06}∑3.00(O16.46⃞1.54)∑18.00. 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

Abstract 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 (Ta0.6⃞0.4)Al6BSi3O18, nioboholite (2012-68), endmember composition (Nb0.6⃞0.4)Al6BSi3O18, and titanoholtite (2012-69), endmember composition (Ti0.75⃞0.25)Al6BSi3O18. (3) Szklaryite (2012-70) with Al1 = ⃞ and an endmember formula ⃞Al6BAs33+O15. 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.

A contribution to understanding the complex nature of peisleyite

Abstract The type specimen of peisleyite has been reinvestigated by a combination of scanning electron microscopy, electron probe microanalysis (EPMA) and synchrotron powder X-ray diffraction. Morphological investigation showed that mats of peisleyite crystals, individually <3 μm across, are intergrown with wavellite veinlets to form the white cryptocrystalline material that is typical of ‘peisleyite’. New EPMA data (mean of 12 analyses) gave the empirical formula of peisleyite as (Na1.69Ca0.18)Σ1.87(Al9.04Fe0.03)Σ9.07[(P6.28S1.38Si0.25)O4]Σ7.91(OH)6.66·27.73H2O, or ideally Na2Al9[(P,S)O4]8(OH)6·28H2O. The associated wavellite was found to be F-rich. Synchrotron powder data were indexed and refined and gave the following unit cell: P1, a = 9.280(19), b = 11.976(19), c = 13.250(18) Å, α = 91.3(1), β = 75.6(1), γ = 67.67(1)º, V = 1308(5) Å3 and Z = 4. These data are significantly different to those reported in the original description of peisleyite.