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The sulfite anion in ettringite-group minerals: a new mineral species hielscherite, Ca3Si(OH)6(SO4)(SO3)·11H2O, and the thaumasite–hielscherite solid-solution series

Published online by Cambridge University Press:  05 July 2018

I. V. Pekov ,
N. V. Chukanov ,
S. N. Britvin ,
Y. K. Kabalov ,
J. Göttlicher ,
V. O. Yapaskurt ,
A. E. Zadov ,
S. V. Krivovichev ,
W. Schüller  and
B. Ternes
I. V. Pekov*
Affiliation:
Faculty of Geology, Moscow State University, Vorobievy Gory, 119991 Moscow, Russia
N. V. Chukanov
Affiliation:
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, 142432 Moscow, Russia
S. N. Britvin
Affiliation:
Faculty of Geology, St Petersburg State University, Universitetskaya Nab. 7/9, St. Petersburg, 199034 Russia, and Nanomaterials Research Centre, Kola Science Center RAS, Fersman Str. 20, 184200 Apatity, Russia
Y. K. Kabalov
Affiliation:
Faculty of Geology, Moscow State University, Vorobievy Gory, 119991 Moscow, Russia
J. Göttlicher
Affiliation:
Karlsruhe Institute of Technology, Institute for Synchrotron Radiation, Hermann von Helmholtz Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany
V. O. Yapaskurt
Affiliation:
Faculty of Geology, Moscow State University, Vorobievy Gory, 119991 Moscow, Russia
A. E. Zadov
Affiliation:
NPP ‘‘Teplokhim’’, Dmitrovskoye Avenue 71, 127238 Moscow, Russia
S. V. Krivovichev
Affiliation:
Faculty of Geology, St Petersburg State University, Universitetskaya Nab. 7/9, St. Petersburg, 199034 Russia, and Nanomaterials Research Centre, Kola Science Center RAS, Fersman Str. 20, 184200 Apatity, Russia
W. Schüller
Affiliation:
Im Strauβenpesch 22, 53518 Adenau, Germany
B. Ternes
Affiliation:
Bahnhofstrasse 45, 56727 Mayen, Germany
*
*E-mail: [email protected]
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Abstract

Hielscherite, ideally Ca3Si(OH)6(SO4)(SO3)·11H2O, (IMA 2011-037) is the first ettringite-group mineral with essential sulfite. We have identified a continuous natural solid-solution series from endmember thaumasite, Ca3Si(OH)6(SO4)(CO3)·12H2O, to a composition with at least 77 mol.% endmember hielscherite. In this series, the SO3:CO3 ratio is variable, whereas the SO4 content remains constant. Compositions with more than 50 mol.% endmember hielscherite have only been found at Graulay quarry near Hillesheim in the western Eifel Mountains, Rhineland-Palatinate, where they occur with phillipsite-K, chabazite-Ca and gypsum in cavities in alkaline basalt. Sulfite-rich thaumasite has been found in hydrothermal assemblages in young alkaline basalts in two volcanic regions of Germany: it is widespread at Graulay quarry and occurs at Rother Kopf, Schellkopf and Bellerberg quarries in Eifel district; it has also been found at Zeilberg quarry, Franconia, Bavaria. Hielscherite forms matted fibrous aggregates up to 1 cm across and groups of acicular to prismatic hexagonal crystals up to 0.3 × 0.3 × 1.5 mm. Individual crystals are colourless and transparent with a vitreous lustre and crystal aggregates are white with a silky lustre. The Mohs hardness is 2–2½. Measured and calculated densities are Dmeas = 1.82(3) and Dcalc = 1.79 g cm–3. Hielscherite is optically uniaxial (–), ω = 1.494(2), ε = 1.476(2). The mean chemical composition of holotype material (determined by electron microprobe for Ca, Al, Si, and S and gas chromatography for C, H and N, with the S4+:S6+ ratio from the crystal-structure data) is CaO 27.15, Al2O3 2.33, SiO2 7.04, CO2 2.71, SO2 6.40, SO3 12.91, N2O5 0.42, H2O 39.22, total 98.18 wt.%. The empirical formula on the basis of 3 Ca atoms per formula unit is Ca3(Si0.73Al0.28)Σ1.01(OH)5.71(SO4)1.00(SO3)0.62(CO3)0.38(NO3)0.05·10.63H2O. The presence of sulfite was confirmed by crystal-structure analysis and infrared and X-ray absorption near edge structure spectra. The crystal structure of sulfite-rich thaumasite from Zeilberg quarry was solved by direct methods based on single-crystal X-ray diffraction data (R1 = 0.064). The structure of hielscherite was refined using the Rietveld method (Rwp = 0.0317). Hielscherite is hexagonal, P63, a = 11.1178(2), c = 10.5381(2) Å, V = 1128.06(4) Å3 and Z = 2. The strongest reflections in the X-ray powder pattern [(d, Å (I)(hkl)] are: 9.62(100)(010,100); 5.551(50)(110); 4.616(37)(012,102); 3.823(64)(112); 3.436(25)(211), 2.742(38)(032,302), 2.528(37)(123,213), 2.180(35)(042,402;223). In both hielscherite and sulfite-rich thaumasite, pyramidal sulfite groups occupy the same site as trigonal carbonate groups, with analogous O sites, whereas tetrahedral sulfate groups occupy separate positions. Hielscherite is named in honour of the German mineral collector Klaus Hielscher (b. 1957).

Keywords

hielscheritenew mineralthaumasiteettringite groupsulfitecrystal structureIR spectroscopyXANES spectroscopyalkaline basaltcementconcreteEifelGraulayZeilberg
Type
Research Article
Information
Mineralogical Magazine , Volume 76 , Issue 5 , October 2012 , pp. 1133 - 1152
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2016

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