Hostname: page-component-5d84bcc8dc-886nk Total loading time: 0 Render date: 2026-08-13T13:53:48.959Z Has data issue: false hasContentIssue false
  • English
  • Français

The hydrocerussite-related phase, NaPb5(CO3)4(OH)3, from the ancient slags of Lavrion, Greece

Published online by Cambridge University Press:  28 February 2018

Oleg I. Siidra ,
Diana O. Nekrasova ,
Nikita V. Chukanov ,
Igor V. Pekov ,
Vasiliy O. Yapaskurt ,
Athanassios Katerinopoulos ,
Panagiotis Voudouris ,
Andreas Magganas  and
Anatoly N. Zaitsev
Oleg I. Siidra*
Affiliation:
Department of Crystallography, St. Petersburg State University, University Embankment 7/9, 199034 St. Petersburg, Russia Nanomaterials Research Center, Kola Science Center, Russian Academy of Sciences, Apatity, Murmansk Region, 184200, Russia
Diana O. Nekrasova
Affiliation:
Department of Crystallography, St. Petersburg State University, University Embankment 7/9, 199034 St. Petersburg, Russia
Nikita V. Chukanov
Affiliation:
Institute of Problems of Chemical Physics, Chernogolovka, Moscow Region, 142432, Russia
Igor V. Pekov
Affiliation:
Faculty of Geology, Moscow State University, Vorobievy Gory, 119991, Moscow, Russia
Vasiliy O. Yapaskurt
Affiliation:
Faculty of Geology, Moscow State University, Vorobievy Gory, 119991, Moscow, Russia
Athanassios Katerinopoulos
Affiliation:
Department of Mineralogy and Petrology, Faculty of Geology and Geoenvironment, National and Kapodistrian University of Athens, Panepistimioupolis 15784 Athens, Greece
Panagiotis Voudouris
Affiliation:
Department of Mineralogy and Petrology, Faculty of Geology and Geoenvironment, National and Kapodistrian University of Athens, Panepistimioupolis 15784 Athens, Greece
Andreas Magganas
Affiliation:
Department of Mineralogy and Petrology, Faculty of Geology and Geoenvironment, National and Kapodistrian University of Athens, Panepistimioupolis 15784 Athens, Greece
Anatoly N. Zaitsev
Affiliation:
Department of Mineralogy, St. Petersburg State University, University Embankment 7/9, 199034 St. Petersburg, Russia
*
*E-mail: o.siidra@spbu.ru
Get access Rights & Permissions [Opens in a new window]

Abstract

The hydrocerussite-related phase, NaPb5(CO3)4(OH)3, has been found as colourless lamellar crystals in cavities within a pebble of the ancient marine slag collected in the Pacha Limani area of the Lavrion mining district, Attiki, Greece. This phase of anthropogenic origin was characterized by electron microprobe, infrared spectroscopy, powder and single-crystal X-ray diffraction. The unique crystal structure (P63/mmc, a = 5.2533(11), c = 29.425(6) Å, V = 703.3(3) Å3 and R1 = 0.047) is based upon structurally and chemically different electroneutral blocks. Each of the blocks can be split into separate sheets. The outer sheets in each block are topologically identical and have the composition [PbCO3]0. The [Pb(OH)2]0 lead hydroxide sheet is sandwiched between the two [PbCO3]0 sheets resulting in the formation of the first block [Pb3(OH)2(CO3)2]0 structurally and compositionally identical to that one in hydrocerussite Pb3(OH)2(CO3)2. Similarly the [Na(OH)]0 sheet is sandwiched between another two [PbCO3]0 sheets thus forming the [NaPb2(OH)(CO3)2]0 block described previously in the structure of abellaite NaPb2(OH)(CO3)2. Stereochemically active lone electron pairs on Pb2+ cations are located between the blocks. There are two blocks of each type per unit cell, which corresponds to the following formula: [Pb3(OH)2(CO3)2][NaPb2(OH)(CO3)2] or NaPb5(CO3)4(OH)3 in the simplified representation. The formation of NaPb5(CO3)4(OH)3 in Lavrion slags is by the contact of lead-rich slags with the sea water over the last two thousand years.

Keywords

hydrocerussiteleadcarbonatecrystal structurelayered structurelone electron pairabellaiteLavrion ancient slagsanthropogenic mineralization

Information

Type
Article
Information
Mineralogical Magazine , Volume 82 , Issue 4 , August 2018 , pp. 809 - 819
Copyright
Copyright © Mineralogical Society of Great Britain and Ireland 2018 

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.)

Article purchase

Temporarily unavailable

Footnotes

Associate Editor: Stuart Mills

References

Anthony, J.W., Bideaux, R.A., Bladh, K.W. and Nichols, M.C. (2003) Handbook of Mineralogy. V. Borates, Carbonates, Sulfates. Mineral Data Publishing, Tucson.Google Scholar
Belokoneva, E.L., Al’-Ama, A.G., Dimitrova, O.V., Kurazhkovskaya, V.S. and Stefanovich, S.Yu. (2002) Synthesis and crystal structure of new carbonate NaPb2(CO3)2(OH). Crystallography Reports, 47, 217–222.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
Giuseppetti, G., Mazzi, F. and Tadini, C. (1990) The crystal structure of leadhillite: Pb4(SO4)(CO3)2(OH)2. Neues Jahrbuch für Mineralogie Monatshefte, 1990, 255–268.Google Scholar
Ibáñez-Insa, J., Elvira, J.J., Llovet, X., Pérez-Cano, J., Oriols, N., Busquets-Masó, M. and Hernández, S. (2017) Abellaite, NaPb2(CO3)2(OH), a new supergene mineral from the Eureka mine, Lleida province, Catalonia, Spain. European Journal of Mineralogy, 29, 915–922.Google Scholar
Kokkoros, P. and Vassiliadis, K. (1953) Röntgenkristallographie von Hydrocerussit. Tschermaks Mineralogische und Petrographische Mitteilungen, 3, 298–304.Google Scholar
Kolitsch, U., Rieck, B., Brandstätter, F., Schreiber, F., Fabritz, K. H., Blaß, G. and Gröbner, J. (2014) Neufunde aus dem altem Bergbau und den Schlacken von Lavrion (II). Mineralien-Welt, 25, 82–95.Google Scholar
Krivovichev, S.V. and Burns, P.C. (2000) Crystal chemistry of basic lead carbonates. III. Crystal structures of Pb3O2(CO3) and NaPb2(CO3)2(OH). Mineralogical Magazine, 64, 1077–1087.Google Scholar
le Page, Y. (1987) Computer derivation of the symmetry elements implied in a structure description. Journal of Applied Crystallography, 20, 264–269.Google Scholar
Libowitzky, E. (1999) Correlation of O–H stretching frequencies and O–H···O hydrogen bond lengths in minerals. Monatshefte für Chemie, 130, 1047–1059.Google Scholar
Martinetto, P., Anne, M., Dooryhée, E., Walter, P. and Tsoucaris, G. (2002), Synthetic hydrocerussite, 2PbCO3·Pb(OH)2, by X-ray powder diffraction. Acta Crystallographica, C58, i82–i84.Google Scholar
Nickel, E.H. and Grice, J.D. (1998) The IMA Commission on New Minerals and Mineral Names: procedures and guidelines on mineral nomenclature, 1998. Mineralogy and Petrology, 64, 237–263.Google Scholar
Palache, C., Berman, H. and Frondel, C. (1951) Dana's System of Mineralogy (7th edition), vol. II. John Wiley, New York.Google Scholar
Rumsey, M.S., Siidra, O.I., Krivovichev, S.V., Spratt, J., Stanley, C.J. and Turner, R.W. IMA 11-G: Plumbonacrite is revalidated. CNMNC Newsletter No. 14, October 2012, page 1288; Mineralogical Magazine, 76, 1281–1288.Google Scholar
Sheldrick, G.M. (2015) New features added to the refinement program SHELXL since 2008 are described and explained. Acta Crystallographica, C71, 3–8.Google Scholar
Shimoni-Livny, L., Glusker, J.P. and Bock, C.W. (1998) Lone pair functionality in divalent lead compounds. Inorganic Chemistry, 37, 1853–1867.Google Scholar
Spek, A.L. (2003) Single-crystal structure validation with the program PLATON. Journal of Applied Crystallography, 36, 7–13.Google Scholar
Siidra, O.I., Britvin, S.N., Krivovichev, S.V., Klimov, D.A. and Depmeier, W. (2014) Crystallography between Kiel and St. Petersburg: review of collaboration and the crystal structure of [Tl5(SiO4)(OH)]2[Tl6(SO4)(OH)4]. Zeitschrift für Kristallographie – Crystalline Materials, 229, 753–759.Google Scholar
Siidra, O.I., Nekrasova, D.O., Depmeier, W., Chukanov, N.V., Zaitsev, A.N. and Turner, R. (2018 a) Hydrocerussite-related minerals and materials: structural principles, chemical variations and infrared spectroscopy. Acta Crystallographica, B74, 182–195.Google Scholar
Siidra, O.I., Jonsson, E., Chukanov, N.V., Nekrasova, D.O., Pekov, I.V., Depmeier, W., Polekhovsky, Yu. S. and Yapaskurt, V.O. (2018 b) Grootfonteinite, Pb3O(CO3)2, a new mineral species from the Kombat mine, Namibia, merotypically related to hydrocerussite. European Journal of Mineralogy, https://doi.org/10.1127/ejm/2018/0030-2723Google Scholar
Steele, I.M., Pluth, J.J. and Livingstone, A. (1998) Crystal structure of macphersonite Pb4SO4(CO3)2(OH)2 comparison with leadhillite. Mineralogical Magazine, 62, 451–459.Google Scholar
Steele, I.M., Pluth, J.J. and Livingstone, A. (1999) Crystal structure of susannite, Pb4SO4(CO3)2(OH)2: a trimorph with macphersonite and leadhillite. European Journal of Mineralogy, 11, 493–499.Google Scholar
Supplementary material: File

Siidra et al. supplementary material

Siidra et al. supplementary material

Download Siidra et al. supplementary material(File)
File 382.8 KB