Hostname: page-component-cd9895bd7-jn8rn Total loading time: 0 Render date: 2024-12-24T02:35:40.056Z Has data issue: false hasContentIssue false

Lead hydrogen citrate monohydrate, Pb(C6H6O7)·H2O, formation during specimen cleaning: a cautionary mineralogical tale

Published online by Cambridge University Press:  05 July 2018

A. R. Kampf*
Affiliation:
Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Blvd, Los Angeles, California 90007, USA
S. J. Mills
Affiliation:
Department of Earth and Ocean Sciences, Universityof British Columbia, Vancouver, British Columbia, Canada V6T 1Z4
*

Abstract

Crystal-structure analysis was used to identify crystals of Pb(C6H6O7)·H2O on a specimen of hematite pseudomorphous after magnetite from the Payύn Matrύ volcanic field, Mendoza Province, Argentina. The compound is triclinic, P, a = 6.3434(2), b = 6.4566(2), c = 12.0640(9) Å, α = 99.233(7), β = 102.810(7), γ = 101.562(7)° and Z=2. The crystal structure, refined to R1 = 0.0169 for 2021 reflections [Fo>4σ(F)], consists of a zig-zag chain of 9-coordinated Pb2+ atoms along b. Chains are linked together by citrate molecules to form thick irregular layers in the ab plane. The layers are linked together only by H bonds. The citrate molecule exhibits normal bond lengths and angles. The Pb2+ atom exhibits markedly lopsided coordination due to the 6s2 lone-electron-pair effect. The lone electron pairs on alternating sets of adjacent Pb2+ atoms in the chain point towards one another.

The formation of the Pb(C6H6O7)·H2O crystals was the result of specimen cleaning in citric acid. The cleaning solution was apparently contaminated through the dissolution of minor associated Pb-bearing species by the citric acid. It is important to be aware of the possibility that micro-crystals may be inadvertently grown on mineral specimens during chemical cleaning, to carefully and critically inspect paragenetic relationships especially when studying mineral specimens that may have been cleaned in chemical agents, and to be particularly aware of health risks when treating Pb-bearing minerals in aqueous citric acid solutions.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2010

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

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M.C., Polidori, G. and Camalli, M. (1994) SIR92 - a program for automatic solution of crystal structures by direct methods. Journal of Applied Crystallography, 27, 435.Google Scholar
Cooper, M.A. and Hawthorne, F. C. (1994) The crystal structure of wherryite, Pb7Cu2(SO4)4(SiO4)2(OH)2, a mixed sulphate-silicate with [[6]M(TO4)2] chains. The Canadian Mineralogist, 32, 373380.Google Scholar
Deganello, S., Kampf, A. R. and Moore, P. B. (1981) The crystal structure of calcium oxalate trihydrate, Ca(H2O)3(C2O4). American Mineralogist, 66, 859865.Google Scholar
Germa, A., Quidelleur, X., Gillot, P.Y. and Tchilinguirian, P. (2010) Volcanic evolution of the back-arc Pleistocene Payun Matru volcanic field (Argentina). Journal of South American Earth Sciences, 29, 717730.CrossRefGoogle Scholar
Kampf, A.R., Housley, R.M., Mills, S.J., Marty, J. and Thome, B. (2010) Lead-tellurium oxysalts from Otto Mountain near Baker, California: I. Ottoite, Pb2TeO5, a new mineral with chains of tellurate octahedra. American Mineralogist, 95, 13291336.CrossRefGoogle Scholar
Kharisun, Taylor M.R., Bevan, D.J.M., Rae, A.D. and Pring, A. (1997) The crystal structure of mawbyite, PbFe2(AsO4)2(OH)2 . Mineralogical Magazine, 61, 685691.CrossRefGoogle Scholar
Kourgiantakis, M., Matzapetakis, M., Raptopoulou, C.P., Terzis, A., and Salifoglou, A. (2000) Lead-citrate chemistry. Synthesis, spectroscopic and structural studies of a novel lead(II)-citrate aqueous complex. Inorganica Chimica Acta, 297, 134138.CrossRefGoogle Scholar
Mills, S.J., Kampf, A.R., Raudsepp, M. and Christy, A.G. (2009) The crystal structure of Ga-rich plumbogummite from Tsumeb, Namibia. Mineralogical Magazine, 73, 837845.CrossRefGoogle Scholar
Mills, S.J., Kolitsch, U., Miyawaki, R., Hatert, F., Poirier, G., Kampf, A.R., Matsubara, S. and Tillmanns, E. (2010) Pb3Fe2(PO4)4(H2O)2, a new octahedral-tetrahedral framework structure with double-strand chains. European Journal of Mineralogy, 22, 595604.CrossRefGoogle Scholar
Moore, P.B. (1988) The joesmithite enigma: Note on the 6s2 Pb2+ lone pair. American Mineralogist, 73, 843844.Google Scholar
Rastsvetaeva, R.K., Pushcharovsky, D.Yu., Furmanova, N.G. and Sarp, H. (1996) Crystal and molecular structure of Cu(II) succinate monohydrate or Never wash copper minerals with detergents. Zeitschrift für Kristallographie, 211, 808811.Google Scholar
Sheldrick, G.M. (2008) A short history of SHELX. Acta Crystallographica, A64, 112122.CrossRefGoogle Scholar
Sokolova, E., Hawthorne, F.C. and Roberts, A.C. (2003) The crystal structure of an anthropogenic Cu-K-Na-hydro-hydroxyl-carbonate-chloride from Jahanngeorggenstadt, Saxony, Germany. The Canadian Mineralogist, 41, 929936.CrossRefGoogle Scholar
Sonmez, M.S. and Kumar, R.V. (2009a) Leaching of waste battery paste components. Part 1: Lead citrate synthesis from PbO and PbO2 . Hydrometallurgy, 95, 5360.CrossRefGoogle Scholar
Sonmez, M.S. and Kumar, R.V. (2009a) Leaching of waste battery paste components. Part 2: Leaching and desulphurization of PbSO4 by citric acid and sodium citrate solution. Hydrometallurgy, 95, 8286.CrossRefGoogle Scholar
Supplementary material: File

Kampf et al. supplementary material

Structure factors

Download Kampf et al. supplementary material(File)
File 93.2 KB
Supplementary material: File

Kampf et al. supplementary material

Cif file

Download Kampf et al. supplementary material(File)
File 16.3 KB