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Research article2008Peer reviewed

Modeling copper(II) complexation in a peat soil based on spectroscopic structural information

Karlsson, Torbjorn; Elgh-Dalgren, Kristin; Skyllberg, Ulf

Abstract

The speciation of Cu in soils and surface waters is largely influenced by complexation reactions with natural organic matter (NOM). In this Study, ion selective electrode data for the binding of Cu2+ to a forest peat soil were collected as a function of equilibration time, pH (2.4-6.6), and total Cu(II) concentration (1-54g Cu kg(-1) dry soil). As a first step, a one-site Langmuir isotherm was successfully fitted to the Cu adsorption data for the complete concentration range at pH 4.6. In a second step, structural information extracted from extended x-ray absorption fine structure (EXAFS) spectroscopy, showing that Cu(II) forms five-membered rings with possible combinations of amine, carboxyl, and carbonyl functional groups in NOM, were used as input for chemical speciation calculations (using the chemical equilibrium model MINTEQA2). In agreement with the EXAFS results, a model consisting of one RNH2, forming monodentate complexes(Cu2+ + RNH2 <-> RH2NCu2+; log stability constant K-RH2NCu(2+) = 9.2; -log acid dissociation constant [pK(a)] = 9.0 for RNH3+), and two adjacent RCOO- groups, forming bidentate complexes (Cu2+ + 2RCOO(-) <-> Cu(OOCR)(2); log stability constant beta((RCOO)2Cu) = 4.7; pK(a) = 4.5 for RCOOH), gave the best fit to the experimental data. Determined stability constants for Cu(II)-amine and Cu(II)-carboxyl complexes were in good agreement with well-defined Cu complexes with amino acids and carboxyls, respectively.

Published in

Soil Science Society of America Journal
2008, Volume: 72, number: 5, pages: 1286-1291
Publisher: SOIL SCI SOC AMER

    UKÄ Subject classification

    Environmental Sciences related to Agriculture and Land-use

    Publication identifier

    DOI: https://doi.org/10.2136/sssaj2007.0390

    Permanent link to this page (URI)

    https://res.slu.se/id/publ/19413