Complexation of f-elements with humic carriers – how dynamic is the equilibrium?

In the far-field of a repository, complexation with dissolved humic matter can be crucial in controlling the mobility of actinides in case of their release [1, 2]. For transport modeling, all interactions in the system metal / humic substance / solid surface are presumed to be dynamic equilibrium processes where association and dissociation run permanently. For metal-humic complexes, however, there are indications of a growing resistance to dissociation over time [3-7]. It is thus questionable whether full reversibility is actually given for this interaction. So far, the existence of a dynamic equilibrium has never been proven. In this study, the isotope exchange principle was employed to gain direct insight into the inner dynamics of the complexation equilibrium, including kinetic stabilization phenomena.

Purified humic acids were contacted with terbium(III) as an analogue of trivalent actinides. The systems contained the radioisotope ¹⁶⁰Tb at a very small amount, whereas concentrations of non-radioactive ¹⁵⁹Tb were varied at a high level, covering a binding isotherm up to the state of saturation. Owing to the high metal loads, flocculation of humic colloids generates a solid-liquid system where adsorbed amounts of ¹⁶⁰Tb can be determined by radiometric analysis of the supernatant. ¹⁵⁹Tb and ¹⁶⁰Tb were introduced simultaneously or consecutively (¹⁵⁹Tb followed by ¹⁶⁰Tb or vice versa). Contact times with both isotopes were varied within a range of 3 months.

In a first series of experiments, ¹⁶⁰Tb was contacted with humic acid that had been pre-equilibrated with ¹⁵⁹Tb at a range of concentrations.
Adsorbed amounts of ¹⁶⁰Tb were found to be equal to those obtained if both isotopes were introduced at the same time, i.e., the radioisotope represented the solid-liquid distribution of total Tb throughout the binding isotherm, including the plateau region where all available binding sites are occupied. Obviously, there is a permanent exchange of free and humic-bound Tb – evidence of a dynamic equilibrium. The rate of exchange was very high, regardless of how long ¹⁵⁹Tb and humic acid had been in contact prior to the addition of ¹⁶⁰Tb. There were no indications of stabilization processes.

Completely different results were obtained if the small amount of ¹⁶⁰Tb (strictly, [¹⁶⁰Tb]Tb) was added first, followed by saturation with non-radioactive ¹⁵⁹Tb. For representing the solid-liquid distribution of total Tb in a dynamic equilibrium, the radioisotope was expected to be partly desorbed since the bound fraction of total Tb is lower in the plateau region of the binding isotherm. Desorption occurred in fact, but at much lower rates than those observed for the equilibration process in the reverse procedure. Moreover, the rates proved to be dependent on the time of pre-equilibration with ¹⁶⁰Tb (increasing hindrance of desorption). The existence of kinetic stabilization processes was thus substantiated. Evidently, they are confined to the most reactive sites, occupied by the radiolabeled fraction of Tb.

Fitting the time-dependent course of isotope exchange according to first-order kinetics was only successful if at least two components with different rate constants were assumed, suggesting that the very small fraction of sites occupied by [¹⁶⁰Tb]Tb (~ 1/10^6) is still only partly affected by the slow exchange kinetics (~ 1/3 slow component).
Nonetheless, this is of relevance since just such extremely low metal loads are to be considered. Extrapolating the fits indicates that it takes up to 2 years until equilibrium is attained. This is, however, a short period compared to the time scale to be covered in predictive transport models. Very low flow velocities must be taken into account.
Therefore, metal exchange between humic carriers and mineral surfaces cannot be neglected, notwithstanding the observed stabilization process since complexation is not restricted in its reversibility.

[1] K. H. Lieser et al., Radiochim. Acta 49, 83 (1990).
[2] G. R. Choppin, Radiochim. Acta 58/59, 113 (1992).
[3] L. Rao et al., Radiochim. Acta 66/67, 141 (1994).
[4] R. Artinger et al., J. Contam. Hydrol. 35, 261 (1998).
[5] S. J. King et al., Phys. Chem. Chem. Phys. 3, 2080 (2001).
[6] H. Geckeis et al., Environ. Sci. Technol. 36, 2946 (2002).
[7] H. Lippold et al., Appl. Geochem. 27, 250 (2012).