Hostname: page-component-78c5997874-ndw9j Total loading time: 0 Render date: 2024-11-19T20:30:12.384Z Has data issue: false hasContentIssue false
  • English
  • Français

Therasiaite, (NH4)3KNa2Fe2+Fe3+(SO4)3Cl5, a new sulfate chloride from La Fossa Crater, Vulcano, Aeolian islands, Italy

Published online by Cambridge University Press:  05 July 2018

F. Demartin ,
C. Castellano  and
I. Campostrini
F. Demartin*
Affiliation:
Università degli Studi di Milano, Dipartimento di Chimica, via Golgi 19, I-20133 Milan, Italy
C. Castellano
Affiliation:
Università degli Studi di Milano, Dipartimento di Chimica, via Golgi 19, I-20133 Milan, Italy
I. Campostrini
Affiliation:
Università degli Studi di Milano, Dipartimento di Chimica, via Golgi 19, I-20133 Milan, Italy
*
*E-mail: [email protected]
Get access Rights & Permissions [Opens in a new window]

Abstract

The new mineral therasiaite, ideally (NH4)3KNa2Fe2+Fe3+(SO4)3Cl5, was found in a mediumtemperature (∼250°C) intracrater active fumarole at La Fossa crater, Vulcano, Aeolian Islands, Sicily, Italy. It occurs on a pyroclastic breccia as brown to dark brown equant to short prismatic crystals up to 0.1 mm in length, in association with salammoniac, kremersite and adranosite. The mineral is monoclinic, space group: Cc (no. 9) with a = 18.284(4), b = 12.073(2), c = 9.535(2) Å, β = 108.10(3)°, V = 2000.6(7) Å3 and Z = 4. The six strongest reflections in the X-ray powder diffraction pattern are: [dobs in Å(I)(hkl)] 2.812(100)(23), 2.664(77)(13), 3.297(28)(33), 3.208(14)(2), 3.008(12)(040), 2.942(11)(331). The empirical formula (based on 17 anions per formula unit (p.f.u.)) is (NH4)2.68K1.32Na2.04Fe1.76Al0.12Mn0.12S2.98O11.95Cl5.05. The measured density is 2.41(1) g cm−3, dcalc = 2.395 g cm−3. The mineral is biaxial (−) with α= 1.585(3) β = 1.615(3) and γ = 1.630(3) (white light). Using single-crystal diffraction data, the structure was refined to a final R(F) = 0.0240 for 5574 independent observed reflections [I > 2σ(I)]. The structure of therasiaite displays a novel topology and contains two independent, distorted octahedral Fe sites, with the Fe atoms in oxidation state 3+ and 2+, respectively, each surrounded by three Cl atoms and three oxygens of the sulfate ions. The Fe octahedra and the three independent sulfate anions are connected to form chains running along [001]. Voids between the chains are occupied by three independent ammonium ions (partially replaced by K+), one K+ and two Na+ ions. The formula resulting from the structure refinement is [(NH4)2.25K0.75]KNa2Fe2(SO4)3Cl5.

Keywords

therasiaitenew mineral speciesfumarole sublimatecrystal structureammoniumsulfatechlorideVulcano islandItaly
Type
Research Article
Information
Mineralogical Magazine , Volume 78 , Issue 1 , February 2014 , pp. 203 - 213
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2014

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Bruker, (2001) SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.Google Scholar
Brese, N.E. and O’Keeffe, M. (1991) Bond-valence parameters for solids. Acta Crystallographica, B47, 192–197.CrossRefGoogle Scholar
Campostrini, I., Demartin, F., Gramaccioli, C.M. and Russo, M. (2011) Vulcano. Tre secoli di mineralogia. Associazione Micro-mineralogica Italiana, Cremona, Italy, 344 pp.Google Scholar
Demartin, F., Gramaccioli, C.M. and Campostrini, I. (2010) Adranosite, (NH4)4NaAl2(SO4)4Cl(OH)2, a new ammonium sulfate chloride from La Fossa Crater, Vulcano, Aeolian Islands, Italy. The Canadian Mineralogist, 48, 315–321.CrossRefGoogle Scholar
Fanfani, L., Nunzi, A., Zanazzi, P.F. and Zanzari, A.R. (1973) The copiapite problem: the crystal structure of a ferrian copiapite. American Mineralogist, 58, 314–322.Google Scholar
Farrugia, L.J. (1999) WinGX suite for small-molecule single-crystal crystallography. Journal of Applied Crystallography, 32, 837–838.CrossRefGoogle Scholar
Hawthorne, F.C., Krivovichev, S.V. and Burns, P.C. (2000) The crystal chemistry of sulfate minerals. Pp. 1–112 in: Sulfate Minerals – Crystallography, Geochemistry, and Environmental Significance (C.N. Alpers, J.L. Jambor, and B.K. Nordstrom, editors). Reviews in Mineralogy and Geochemistry, 40. Mineralogical Society of America, Washington DC and the Geochemical Society, St Louis, Missouri, USA.CrossRefGoogle Scholar
Holland, T.J.B. and Redfern, S.A.T. (1997) Unit cell refinement from powder diffraction data: the use of regression diagnostics. Mineralogical Magazine, 61, 65–77.CrossRefGoogle Scholar
Khan, A.A. and Baur, W.H. (1972) Salt hydrates. VIII. The crystal structures of sodium ammonium orthochromate dihydrate and magnesium diammonium bis(hydrogen orthophosphate) tetrahydrate and a discussion of the ammonium ion. Acta Crystallographica, B28, 683–693.CrossRefGoogle Scholar
Majzlan, J. and Michallik, R. (2007) The crystal structures, solid solutions and infrared spectra of copiapite-group minerals. Mineralogical Magazine, 71, 553–569.CrossRefGoogle Scholar
Mandarino, J.A. (1981) The Gladstone-Dale relationship. IV. The compatibility index and its application. The Canadian Mineralogist, 19, 441–450.Google Scholar
Mitolo, D., Demartin, F., Garavelli, A., Campostrini, I., Pinto, D., Gramaccioli, C.M., Acquafredda, P. and Kolitsch, U. (2013) Adranosite-(Fe), (NH4)4NaFe2(SO4)4Cl(OH)2, a new ammonium chloride from La Fossa Crater, Vulcano, Aeolian Islands, Italy. The Canadian Mineralogist, 51, 57–66.CrossRefGoogle Scholar
Sheldrick, G.M. (2000) SADABS Area-Detector Absorption Correction Program, Bruker AXS Inc., Madison, Wisconsin, USA.Google Scholar
Sheldrick, G.M. (2008) A short history of SHELX. Acta Crystallographica, A64, 112–122.CrossRefGoogle Scholar
Spek, A.L. (2003) Single-crystal structure validation with the program PLATON. Journal of Applied Crystallography, 36, 7–13.CrossRefGoogle Scholar
Zhou, Jingliang, Li, Jiaiju and Dong, Wei (1988) The crystal structure of xitieshanite. Kexue Tongbao (Chinese Science Bulletin), 33, 502–505.Google Scholar
Supplementary material: File

Demartin et al. supplementary material

CIF

Download Demartin et al. supplementary material(File)
File 36.9 KB