Hostname: page-component-8448b6f56d-qsmjn Total loading time: 0 Render date: 2024-04-24T10:52:24.286Z Has data issue: false hasContentIssue false
  • English
  • Français

Pb2(AsO2OH)Cl2, a new phase from the Lavrion ancient slags, Greece: occurrence and characterization

Published online by Cambridge University Press:  05 July 2018

O. I. Siidra ,
N. V. Chukanov ,
I. V. Pekov ,
S. V. Krivovichev ,
A. Magganas ,
A. Katerinopoulos  and
P. Voudouris
O. I. Siidra*
Affiliation:
Department of Crystallography, Geological faculty, Saint Petersburg State University, University emb. 7/9, St Petersburg, 199034, Russia
N. V. Chukanov
Affiliation:
Institute of Problems of Chemical Physics, Chernogolovka, Moscow 142432, Russia
I. V. Pekov
Affiliation:
Faculty of Geology, Moscow State University, Vorob’evy Gory, GSP-2, Moscow 119992, Russia
S. V. Krivovichev
Affiliation:
Department of Crystallography, Geological faculty, Saint Petersburg State University, University emb. 7/9, St Petersburg, 199034, Russia
A. Magganas
Affiliation:
Department of Mineralogy and Petrology, Faculty of Geology and Geoenvironment, National and Kapodistrian University of Athens, Panepistimioupolis 15784, Athens, Greece
A. Katerinopoulos
Affiliation:
Department of Mineralogy and Petrology, Faculty of Geology and Geoenvironment, National and Kapodistrian University of Athens, Panepistimioupolis 15784, Athens, Greece
P. Voudouris
Affiliation:
Department of Mineralogy and Petrology, Faculty of Geology and Geoenvironment, National and Kapodistrian University of Athens, Panepistimioupolis 15784, Athens, Greece
*
E-mail: siidra@mail.ru
Get access Rights & Permissions [Opens in a new window]

Abstract

Transparent prismatic crystals of Pb2(AsO2OH)Cl2 were collected in black metallurgical slag on the coast in the Punta Zeza area, 3 km south of the town of Lavrion, Greece. Analyses by energy-dispersive X-ray spectrometry (EDS) provided the following chemical composition: PbO 73.04, As2O3 15.97, Cl 11.42, O=Cl –2.58, total 97.85 wt.%. The empirical formula calculated on the basis of As = 1 is HxPb2.03(AsO3)1.00Cl1.995 (x = 0.96). The infrared spectrum of Pb2(AsO2OH)Cl2 has characteristic AsO33– bands at 707 and 594 cm–1, O–H stretching vibrations at 3310 and 2900 cm–1 and a band at 1107 cm–1 which is assigned to As–O–H bending vibrations. The structure, which is monoclinic P21/m, a = 6.4235(8), b = 5.5399(7), c = 9.321(1) Å, β = 90.767(2)°, V = 331.67(7) Å3, R1 = 0.035, is identical to that of synthetic Pb2(AsO2OH)Cl2 and contains two symmetrically unique Pb sites and one As site. The crystal structure is based on [Pb2AsO2OH]2+ double chains interconnected via weak Pb–Cl bonds to produce a three-dimensional framework which is closely related to that of Pb oxysalt minerals containing [O2Pb3]2+ chains of oxocentred [OPb4]6+ tetrahedra including mendipite, damaraite, rickturnerite and plumboselite.

Keywords

lead arseniteprotonated oxoanionscrystal structureLavrionancient slag
Type
Research Article
Information
Mineralogical Magazine , Volume 76 , Issue 3 , June 2012 , pp. 597 - 602
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2016

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

Brese, N.E. and óKeeffe, M. (1991) Bond-valence parameters for solids. Act Crystallographica, B47, 192—197 CrossRefGoogle Scholar
Brown, I.D. (1974) Bond valence as an aid to understanding the stereochemistry of O and F complexes of Sn(II), Sb(III), Te(IV), I(V) and Xe(VI). Journal of Solid Stat. Chemistry, 11, 214—233 Google Scholar
Effenberger, H., Miletich, R. and Pertlik, F. (1990) Structure of dilead(II) hydrogenarsenate(III) dichloride. Act Crystallographica, C46, 541—543 Google Scholar
Ferraris, G. and Ivaldi, G. (1984) X-OH and O-H_O bond lengths in protonated oxoanions. Acta Crystallographica, B40, 1—6.Google Scholar
Gelaude, P., van Kalmthout, P. and Rewitzer, C. (1996) Laurion: The Minerals in the Ancient Slags. Janssen Print, Nijmegen, The Netherlands..Google Scholar
Jensen, W.B. (1980). The Lewis Acid-base Concepts: an Overview. Wiley, New York..Google Scholar
Kampf, A.R., Mills, S.J. and Pinch, W.W. (2011) Plumboselite, Pb3O2(SeO3), a new oxidation zone mineral from Tsumeb, Namibia. Mineralogy and Petrology, 101, 75—80 CrossRefGoogle Scholar
Keller, P., Lissner, F. and Schleid, T. (2001) Damaraite, Pb3O2(OH)Cl: crystal structure and new chemical formula. Neues Jahrbuch fü r Mineralogie. Monatshefte, 2001, 326—336 Google Scholar
Krivovichev, S.V. (2008) Structural Crystallography of Inorganic Oxysalts. Oxford University Press, Oxford, UK.Google Scholar
Krivovichev, S.V. and Brown, I.D. (2001) Are the compressive effects of encapsulation an artifact of the bond valence parameters? Zeitschrift f. Kristallographie, 216, 245—247 Google Scholar
Krivovichev, S.V. and Burns, P.C. (2001) Crystal chemistry of lead oxide chlorides. I. Crystal structures of synthetic mendipite, Pb3O2Cl2, and synthetic damaraite, Pb3O2(OH)Cl. Europea. Journal of Mineralogy, 13, 801—809 CrossRefGoogle Scholar
Krivovichev, S.V. and Burns, P.C. (2002) Crystal chemistry of lead oxide chlorides. II. Crystal structure of Pb7O4(OH)4Cl2. Europea. Journal of Mineralogy, 14, 135—140 CrossRefGoogle Scholar
Krivovichev, S.V., Avdontseva, E.Yu. and Burns, P.C. (2004) Synthesis and crystal structure of Pb3O2(SeO3). Zeitschrift für Anorganische und Allgemein. Chemie, 630, 558—562 Google Scholar
Nickel, E.H. (1995) Definition of a mineral. Europea. Journal of Mineralogy, 7, 1213—1215 CrossRefGoogle Scholar
Rumsey, M.S., Krivovichev, S.V., Siidra, O.I., Kirk, C.A., Stanley, C.J. and Spratt, J. (2012) Rickturnerite: Pb7O4[Mg(OH)4](OH)Cl3 a complex new Pb oxychloride mineral. Mineralogical Magazine, 76, 59—73.CrossRefGoogle Scholar
Sheldrick, G.M. (2008) A short history of SHELX. Act Crystallographica, A64, 112—122 CrossRefGoogle Scholar
Siidra, O.I., Krivovichev, S.V. and Filatov, S.K. (2008a) Minerals and synthetic Pb(II) compounds with oxocentered tetrahedra: review and classification. Zeitschrift für Kristallographie, 223, 114—126 Google Scholar
Siidra, O.I., Krivovichev, S.V., Armbruster, T. and Depmeier, W. (2008b) Crystal chemistry of the mendipite-type system Pb3O2Cl2-Pb3O2Br2. Zeitschrift für Kristallographie, 223, 204—211 CrossRefGoogle Scholar
Siidra, O.I., Krivovichev, S.V., Turner, R. and Rumsey, M.S. (2008c) Chloroxiphite Pb3CuO2(OH)2Cl2: structure refinement and description in terms of oxocentred OPb4 Tetrahedra. Mineralogical Magazine, 72, 793—798 CrossRefGoogle Scholar
Siidra, O.I., Krivovichev, S.V. and Depmeier, W. (2008d) Crystal chemistry of natural and synthetic lead oxohalides: II. Crystal structure of Pb7O4(OH)4Br2. Geology of Ore Deposits, 50, 801—805 CrossRefGoogle Scholar
Siidra, O.I., Krivovichev, S.V., Chukanov, N.V., Pekov, I.V., Magganas, P., Katerinopoulos, A. and Voudouris, P. (2011) The crystal structure of Pb5(As3+O3)Cl7 from ancient slags of Lavrion, Greece - a novel Pb(II) chloride arsenite. Mineralogica. Magazine, 75, 339—348 Google Scholar