Free Eu(III) Determination by Donnan Membrane Technique with Electrochemical Detection: Implementation and Evaluation

The aim of this study was to develop an analytical method to determine free concentrations of Europium (Eu(III)) in natural waters. Europium(III) in solution was detected using cathodic stripping voltammetry after complexation with N-nitroso-N-phenylhydroxylamine (cupferron). Optimization of analytical parameters allowed us to detect nanomolar levels of Eu(III) in solution. Free Eu(III) in solution was measured using the Donnan membrane technique in which a natural solution (the “donor”, containing various ligands) is separated from a ligand-free solution (the “acceptor”) by a cation-exchange membrane. This membrane allows only non-colloidal cationic species to pass through it, and after an adequate time equilibrium is reached between both compartments. Total Eu(III) concentration can then be quantified in the acceptor solution and related to free Eu(III) in the natural sample. Due to its high valency, free Eu(III) tends to adsorb strongly to the cation-exchange membrane. In order to determine the physicochemical conditions minimizing this adsorption, we analyzed solutions of different Eu(III) and Ca(II) (as background ion) concentrations. Results showed that 100 mM of Ca(II) were necessary to make adsorption of Eu(III) onto the membrane negligible. The optimized setup was then used to quantify Eu(III) complexation in a Eu(III)-dissolved organic matter solution.

Strategies in the application of the Donnan membrane technique

Environmental context Free ion concentrations determine the effects of nutrients and pollutants on organisms in the environment. The Donnan membrane technique provides a measure of free ion concentrations. This paper presents clear guidelines on the application of the Donnan membrane technique for determining free ion concentrations in both synthetic and natural samples. Abstract The Donnan membrane technique (DMT) can be applied to measure free ion concentrations both in laboratory and in situ in the field. In designing DMT experiments, different strategies can be taken, depending on whether accumulation is needed. (1) When the free ion concentration is above the detection limit of the analytical technique (e.g. ICP-MS), no accumulation is needed and no ligand is added to the acceptor. Measurement can be based on the Donnan membrane equilibrium. (2) When an accumulation of less than 500 times is needed, an appropriate amount of ligand can be added to the acceptor and measurement can be based on the Donnan membrane equilibrium. (3) When an accumulation factor of larger than 500 times is needed, a relatively large amount of ligand is added to the acceptor and measurement can be based on the transport kinetics. In this paper, several issues in designing the DMT experiments are discussed: choice of DMT cell, measurement strategies and ligands and possible implication of slow dissociation of metal complexes in the sample solution (lability issue). The objective of this paper is to give better guidance in the application of DMT for measuring free ion concentrations in both synthetic and natural samples.