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

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Footnotes

Associate Editor: Stuart Mills

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