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The missing sulphur in mattheddleite, sulphur analysis of sulphates, and paragenetic relations at Leadhills, Scotland

Published online by Cambridge University Press:  05 July 2018

E. J. Essene ,
C. E. Henderson  and
A. Livingstone
E. J. Essene*
Affiliation:
Department of Geological Sciences, University of Michigan, Ann Arbor MI 48109-1063, USA
C. E. Henderson
Affiliation:
Department of Geological Sciences, University of Michigan, Ann Arbor MI 48109-1063, USA
A. Livingstone
Affiliation:
6, St. Ronan's Terrace, Innerleithen, Peeblesshire EH44 6RB, UK
*
*E-mail: essene@umich.edu
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Abstract

Published electron microprobe analyses of mattheddleite, a lead sulpho-silicate apatite from Leadhills, Scotland, have 9–13% IV site deficiencies. However, galena was used as a standard for S, which suggested that low S resulted from a shift in the S-Kα peak. Wavelength scans with a PET crystal show that the S-Kα peak is shifted down by 0.0026 Å for sulphates relative to sulphides. Quantitative analyses show a ∼30% increase of S in mattheddleite using a celestite standard, which fills the IV site, but with Si > S, on average Pb5S1.2Si1.8O11.7Cl0.6(OH)0.4. Direct analysis of oxygen with the electron microprobe implies that the charge imbalance engendered from the inequality of Si and S is compensated with substitution of a vacancy (□), as in Pb5S1.2Si1.8[O11.7□0.3] [Cl0.6(OH)0.4] or Pb5S1.2Si1.8[O11.7(Cl, OH)0.73]. [Cl,OH)0.7 □0.3]. Calculation of OH as l–C1 suggests the presence of both OH- and Cl-dominant mattheddleite at Leadhills, but direct analysis of H is needed to confirm the dominance of OH in the channel site. Wavelength-dispersive analyses of S in apatite and other sulphates must be undertaken with sulphate standards: use of sulphide standards yields a negative error on the order of 10–20% in the resultant S concentration. Reactions of mattheddleite with other Pb minerals at Leadhills show that their stability depends on fluid composition as well as pressure and temperature. An X-ray map of Cl shows complex zoning between Cl-poor and Cl-rich mattheddleite, recording rapid changes in the fluid chemistry during late-stage hydrothermal processes at Leadhills.

Keywords

mattheddleitesulphateapatitewavelength shiftCl migrationLeadhillsphase equilibria
Type
Research Article
Information
Mineralogical Magazine , Volume 70 , Issue 3 , June 2006 , pp. 265 - 280
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2006

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