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An investigation of extreme silver enrichment at tennantite surfaces exposed to alkaline solutions: an XPS-based study

Published online by Cambridge University Press:  05 July 2018

E. L. Hobson ,
P. Wincott ,
D. J. Vaughan  and
R. A. D. Pattrick
P. Wincott
Affiliation:
School of Earth, Atmospheric and Environmental Sciences, and Williamson Research Centre for Molecular Environmental Science, University of Manchester, Oxford Road, Manchester M13 9PL, UK
D. J. Vaughan
Affiliation:
School of Earth, Atmospheric and Environmental Sciences, and Williamson Research Centre for Molecular Environmental Science, University of Manchester, Oxford Road, Manchester M13 9PL, UK
R. A. D. Pattrick
Affiliation:
School of Earth, Atmospheric and Environmental Sciences, and Williamson Research Centre for Molecular Environmental Science, University of Manchester, Oxford Road, Manchester M13 9PL, UK
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Abstract

Extreme silver enrichment at the surface of the complex sulphide, tennantite (ideal formula: Cu12As4S13), occurs following exposure to alkaline solutions, and involves the development of an Ag-rich sulphide surface species. The tennantite has a low bulk Ag content of 0.3 at.%, and a percentage surface enrichment of Ag is thirty-six times that of the bulk. The techniques of X-ray photoelectron spectroscopy (XPS) and reflection extended X-ray absorption fine structure spectroscopy show the new phase to be a Ag sulphide species compositionally similar to cupriferous proustite ((Cu,Ag)3AsS3). Solution experiments and XPS depth profiling show that the surface is most depleted in Cu and Zn, and enriched in Ag compared to the bulk tennantite. Selective dissolution and reprecipitation at the tennantite surface cannot explain the enrichment of Ag relative to the bulk. Migration must have occurred and could have been driven by the leaching out of Cu which produces a metal-depleted surface, coupled to the relative incompatibility of Ag in the tennantite lattice. To account for the extreme enrichment at the surface, Ag must have diffused from depths of up to 9 nm, probably via structural weaknesses and vacancies in the tennantite lattice.

Keywords

tennantitetetrahedriteAgdiffusionmigrationenrichmentXPSleachingalkaline solutionssurfaceREFLEXAFS
Type
Editorial
Information
Mineralogical Magazine , Volume 70 , Issue 4 , August 2006 , pp. 445 - 457
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2006

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