Dynamic features of speciation analysis by adsorptive stripping techniques

Raewyn M. Town; Herman P. van Leeuwen

doi:10.1071/EN10027

RESEARCH ARTICLE

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Dynamic features of speciation analysis by adsorptive stripping techniques

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

+ Author Affiliations

- Author Affiliations

^A Institute for Physics and Chemistry, University of Southern Denmark, Campusvej 55, DK-5230 Odense, Denmark.

^B Laboratory of Physical Chemistry and Colloid Science, Wageningen University, Dreijenplein 6, 6703 HB Wageningen, The Netherlands.

^C Corresponding author. Email: rmt@ifk.sdu.dk

Environmental Chemistry 7(3) 242-249 https://doi.org/10.1071/EN10027
Submitted: 17 March 2010 Accepted: 28 April 2010 Published: 22 June 2010

Environmental context. The environmental fate and bioavailability of metal ions in natural waters is determined by their thermodynamic stability and kinetic features, both of which are distributed. Competing ligand exchange – adsorptive stripping (CLE-AdS) is a technique that measures a certain portion of these complexes as determined by the stability of the selected competing ligand and the dynamic features of the sample complexes that remain following ligand exchange. Exploitation of CLE-AdS to determine a spectrum of sample complexes requires insight into its thermodynamic and kinetic windows.

Abstract. The kinetic features of the accumulation step of competing ligand exchange – adsorptive stripping (CLE-AdS) in metal speciation methodology are elaborated. During the adsorptive accumulation process, the flux of the surface active complex ML_ad towards the electrode may be modified by the coupled conversions of ML and M into ML_ad. An immediate consequence is that the accumulation flux of ML_ad can be greater than that corresponding to its mere bulk concentration: a labile ML contributes fully to the ML_ad accumulation, and a further flux enhancement can arise if ML is more mobile than ML_ad (D_ML > D_{ML_ad}). Applying the conventional lability criterion, we present a framework for interpretation of CLE-AdS measurements in the presence of kinetic contributions from sample ML to the adsorptive accumulation of ML_ad. Measured accumulation fluxes for a kinetic case are well described by the presented theoretical framework. The dynamic analysis provides the basis for exploitation of CLE-AdS over a wider kinetic window than has been used to date. Consideration of the dynamics of sample species during the adsorptive accumulation step is fundamental for interpretation of metal speciation by CLE-AdS in complex natural systems that contain a distribution of complexes of different stability, lability, and mobility.

Additional keywords: chronopotentiometry, dynamic speciation, kinetic window, voltammetry.

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Dynamic features of speciation analysis by adsorptive stripping techniques

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