Modelling Eu(III) speciation in a Eu(III)/PAHA/α-Al2O3 ternary system

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In this work, modelling of Eu(III) speciation in a ternary system, i.e., in presence of purified Aldrich humic acid (PAHA) and α-Al2O3, is presented. First, the mineral surface charge is measured by potentiometric titrations and then described using the CD–MUSIC model. This model is also used to describe Eu(III) binding to the α-Al2O3 surface at different pH values, ionic strength and mineral concentrations. Time-resolved luminescence spectroscopy (TRLS) is then used to study the binding of Eu(III) to PAHA at pH 4 with different humic acid concentrations. The spectra are used to calculate a spectroscopic “titration curve”, used to determine Eu(III)/PAHA binding parameters in the NICA-Donnan model. Following a previous study (Janot et al., Water Res. 46, 731–740), modelling of the ternary system is based upon the definition of two PAHA pools where one fraction remains in solution and the other is adsorbed onto the mineral surface, with each possessing different proton and metal binding parameters. The modification of protonation behaviour for both fractions is examined using spectrophotometric titrations of the non-adsorbed PAHA fraction at different organic/mineral ratios. These data are then used to describe Eu(III) interactions in the ternary system: Eu(III) repartitioning in the ternary system is calculated for different pH, ionic strength and PAHA concentrations, and results are compared to experimental observations. The model is in good agreement with experimental data, except at high PAHA fractionation rates. Results show that organic complexation dominates over a large pH range, with the predominant species existing as the surface-bound fraction. Above pH 8, Eu(III) seems to be mostly complexed to the mineral surface, which is in agreement with previous spectroscopic observations (Janot et al., Environ. Sci. Technol. 45, 3224–3230).