EXAFS study of the inner shell structure in copper(II) complexes with humic substances

Gregory V. Korshin, Anatoly I. Frenkel, Edward A. Stern

Research output: Contribution to journalArticlepeer-review

124 Scopus citations

Abstract

The structure of humic substances (HS) and their complexes with metal cations is a matter of ongoing debate. In this paper, the structure of Cu2+-HS complexes was studied by extended X-ray absorption fine structure spectroscopy (EXAFS). This method is highly sensitive to the local structure around the target (e.g., Cu2+ or other cations). The CuO6 octahedron was used to model the inner complexation shell of the Cu2+-HS complexes. The quality of the fit of the EXAFS data was tested using model systems (copper(II)-aqua and -salicylate complexes). On the basis of the dissimilarity of the EXAFS spectra for the Cu2+- tetrahydrofurantetracarboxylic acid complex from those of the Cu2+-HS complexes, it is concluded that complexation sites of HS are not likely to contain carboxylic groups attached to a furan ring. The Cu-O distances all Cu2+-HS complexes were shorter than those in aqua or salicylate complexes. The contraction of the Cu-O distance was especially prominent for the axial direction, and the distortion of the inner shell was much reduced. The mean- square disorder values for the axial Cu-O pairs in Cu2+-HS complexes indicate that the axial oxygens are more tightly bound with the central cation than those in either aqua or salicylic complexes, possibly indicating six-dentate coordination of Cu2+ by HS.

Original languageEnglish
Pages (from-to)2699-2705
Number of pages7
JournalEnvironmental Science and Technology
Volume32
Issue number18
DOIs
StatePublished - 15 Sep 1998
Externally publishedYes

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