Environmental Chemistry Environmental Chemistry Society
Environmental problems - Chemical approaches
RESEARCH FRONT

Labilities of aqueous nanoparticulate metal complexes in environmental speciation analysis

Raewyn M. Town A C and Herman P. van Leeuwen B

A Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, DK-5230 Odense, Denmark.

B Laboratory of Physical Chemistry and Colloid Science, Wageningen University, Dreijenplein 6, NL-6703 HB Wageningen, the Netherlands.

C Corresponding author. Email: raewyn.town@sdu.dk

Environmental Chemistry 11(2) 196-205 http://dx.doi.org/10.1071/EN13138
Submitted: 20 July 2013  Accepted: 10 October 2013   Published: 25 March 2014

Environmental context. Sorbing nanoparticles can have a significant effect on the speciation of small ions and molecules in the environment. The reactivity of nanoparticulate-bound species can differ significantly from that of their molecular or colloidal counterparts. We present a conceptual framework that describes the chemodynamics and lability of nanoparticulate metal complexes over a wide range of experimental timescales and environmental conditions.

Abstract. An inherent property of a dispersion of charged nanoparticles is that their charges and reactive sites are spatially confined to the particle body which is at a different potential from that in the bulk medium. This feature has important consequences for the reactivity of nanoparticulate complexants: the diffusive rate of reactant supply is lower as compared to molecular complexants, whereas the local concentration of reactant ions may be enhanced if the particle’s electric field has the opposite charge sign. These effects are most dramatic for soft nanoparticles for which the electrostatic accumulation mechanisms operate on a 3-D level. We show how the interplay of these effects governs the reactivity of charged nanoparticulate metal complexes (M-NPs) at the surface of an analytical speciation sensor. A theoretical framework is presented that describes the lability of M-NP species over a range of effective timescales for different electrochemical and other dynamic speciation analysis techniques. The concepts are illustrated by electrochemical stripping data on metal complexes with natural soft nanoparticles of humic acid.

Additional keywords: humic acid, kinetics, lability, stripping chronopotentiometry.


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