Impact of pH on CdII partitioning between alginate gel and aqueous media
Erwin J. J. Kalis A , Thomas A. Davis B , Raewyn M. Town C D and Herman P. van Leeuwen AA Laboratory of Physical Chemistry and Colloid Science, Wageningen University, Dreijenplein 6, 6703 HB Wageningen, the Netherlands.
B Department of Chemistry, University of Montreal, Succursale Centre-Ville, Montreal, QC, H3C 3J7, Canada.
C Institute for Physics and Chemistry, University of Southern Denmark, Campusvej 55, 5230 Odense, Denmark.
D Corresponding author. Email: rmt@ifk.sdu.dk
Environmental Chemistry 6(4) 305-310 https://doi.org/10.1071/EN09060
Submitted: 17 May 2009 Accepted: 1 July 2009 Published: 25 August 2009
Environmental context. Biogels, such as those in cell walls or biofilm matrices, generally comprise negative structural charge which leads to accumulation of positively charged species, e.g. metal ions. The magnitude of the effective charge, and hence the local chemical speciation within the gel phase, is pH dependent. In situ speciation measurements in biogels, such as the model alginate studied in this work, offer a better estimate of bioavailable concentrations than does analysis of the surrounding aqueous medium.
Abstract. Many microorganisms exist in a biogel-mediated micro-environment such as a cell wall or a biofilm, in which local concentrations of ionic nutrients and pollutants differ from those in the surrounding bulk medium. The local concentration is the relevant parameter for considerations of bioavailability. These modified concentrations arise as a consequence of the negative charges within biogels which may induce a Donnan potential inside the biogel phase. For metals, the net effect on the speciation within the biogel, relative to the bulk medium, is an enhancement of the concentration of free cations. Since the structural charge in the biogel arises from protolytic functional groups, the Donnan potential is pH dependent. Here we apply in situ voltammetry to measure the free metal ion concentration inside alginate gel as a function of pH. In the pH range 3 to 7, the speciation of CdII within this model biogel can be explained by specific binding to carboxylic functional groups and electrostatic binding resulting from the Donnan potential.
Acknowledgements
This study was performed within the framework of the ECODIS project funded by the European Commission’s sixth framework program, subpriority 6.3 ‘Global change and Ecosystems’, under contract 518043. Dr J. P. Pinheiro is gratefully acknowledged for his contribution to the early development of voltammetric measurements in gel phases along with Profs. Bjørn Sundby, George W. Luther III and Dr Cédric Magen. We also gratefully acknowledge early discussions on the topic of alginate gels with Dr Synnøve Holtan, Dr Kurt I. Draget and Prof. Olav Smidsrød, Department of Biotechnology, NTNU, Trondheim, Norway.
Figures showing: (i) information obtained from the diffusion-limited steady-state Cd voltammograms for an alginate gel-solution system in Donnan equilibrium; (ii) bound Ca content and bound protons of alginate gel as a function of pH; (iii) Ca content of alginate gel before and after acidification; and (iv) relative alginate gel density as a function of pH are given. This information is available free of charge on the journal website at http://www.publish.csiro.au/?act=view_file&file_id=EN09009_AC.pdf.
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