Physics
Scientific paper
May 1997
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1997gecoa..61.2023p&link_type=abstract
Geochimica et Cosmochimica Acta, Volume 61, Issue 10, p. 2023-2036.
Physics
10
Scientific paper
X-ray absorption (XAS) and X-ray photoelectron spectroscopy (XPS) analysis of copper sulfide precipitated from aqueous solution at ambient temperatures reveals the existence of a metastable primitive structure that ages to a structure with the characteristics of amorphous covellite; XAS provides direct structural information on the structure of these amorphous copper sulfides. Extended X-ray absorption fine structure (EXAFS) analysis of the primitive structure demonstrates the presence of disulfide (S2-groups) and a CuS interaction of 2.8Å: the latter is not found in covellite. Copper K-edge X-ray absorption near-edge structure (XANES) indicates the dominance of 3- over 4-coordinate Cu in the primitive phase, while Cu L3-edge spectra reveal only Cu(I) to be present in all precipitates formed. XPS data confirm the presence of only Cu(I) and reveal that three types of S are present. Upon ageing, the primitive structure transforms to one with the characteristics of covellite, and this transformation involves the reordering of the S2- and Cu3SCuS3-layers. Development of the primitive phase from either a wurtzite-like structure or planar Cu3SCuS3-layers is possible, with the structural evolution driven by the antipathy of Cu(II) for tetrahedral coordination and anomalous electron densities in the metastable structures.
Charnock John M.
England Katharine E. R.
Garner David C.
Helz George R.
Mosselmans Fred W. J.
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