Extended X-ray absorption fine structure spectroscopy evidence for the complexation of cadmium by reduced sulfur groups in natural organic matter

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Karlsson, Torbjörn (författare)

Extended X-ray absorption fine structure spectroscopy evidence for the complexation of cadmium by reduced sulfur groups in natural organic matter

Artikel/kapitelEngelska2005

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2005-03-19
American Chemical Society (ACS),2005
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LIBRIS-ID:oai:DiVA.org:umu-13515
https://urn.kb.se/resolve?urn=urn:nbn:se:umu:diva-13515URI
https://doi.org/10.1021/es048585aDOI

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Språk:engelska
Sammanfattning på:engelska

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Ämneskategori:art swepub-publicationtype

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It is widely accepted that the bioavaiiability, toxicity, and mobility of trace metals are highly dependent on complexation reactions with functional groups in natural organic matter (NOM). In this study, the coordination chemistry of Cd in NOM was investigated by extended X-ray absorption fine structure spectroscopy. Soil organic matter (SOM) from different types of organic soils and dissolved organic matter (DOM) from an organic and a mineral soil horizon of a Spodosol and aquatic DOM from Suwannee River were investigated. In SOM samples (1000-25000 mu g of Cd g(-1), pH 4.6-6.6), Cd was coordinated by 1.0-2.5 S atoms at a distance of 2.49-2.55 angstrom and by 3.0-4.5 O/N atoms at a distance of 2.22-2.25 angstrom. In DOM samples (1750-4250 mu g of Cd g(-1), pH 5.4-6.3), Cd was coordinated by 0.3-1.8 S atoms at a distance of 2.51-2.56 angstrom and 3.6-4.5 O/N atoms at a distance of 2.23-2.26 angstrom. In both SOM and DOM samples a second coordination shell of 1.7-6.0 carbon atoms was found at an average distance of 3.12 angstrom. This is direct evidence for inner-sphere complexation of Cd by functional groups in NOM. Furthermore, ion activity measurements showed that less than 1% of total Cd was in the form of free Cd2+ in our samples. Bond distances and coordination numbers suggest that Cd complexed in SOM and DOM is a mixture of a 4-coordination with S (thiols) and 4- and 6-coordinations with O/N ligands. Given that Cd-S associations on average are stronger than Cd-O/N associations, our results strongly indicate that reduced S ligands are involved in the complexation of Cd by NOM also at native concentrations of metal in oxidized organic-rich soils and in humic streams.

Ämnesord och genrebeteckningar

SOIL HUMIC SUBSTANCES
BINDING-SITES
METHYL MERCURY
FULVIC-ACIDS
CD-113 NMR
COORDINATION
SPECIATION
LIGANDS
EXAFS
WATERS

Biuppslag (personer, institutioner, konferenser, titlar ...)

Persson, PerUmeå universitet,Kemiska institutionen(Swepub:umu)pepe0002 (författare)
Skyllberg, Ulf (författare)
Umeå universitetKemiska institutionen (creator_code:org_t)

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Ingår i:ENVIRONMENTAL SCIENCE & TECHNOLOGY: American Chemical Society (ACS)39:9, s. 3048-550013-936X1520-5851

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Av författaren/redakt...: Karlsson, Torbjö ...; Persson, Per; Skyllberg, Ulf

Artiklar i publikationen: ENVIRONMENTAL SC ...

Av lärosätet: Umeå universitet

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