Gd-DTPA in the hydrosphere: Kinetics of transmetallation by ions of rare earth elements, Y and Cu

The kinetics of transmetallation of Gd3+ in diethylenetriaminpentaacetic acid (Gd-DTPA) by rare earth elements (except Yb), Y3+ and Cu2+ has been studied in test solutions ranging from pH 5 to 6.5 in order to understand the distribution and longevity of their chelates in the hydrosphere. Chelated and non-chelated species were separated by adsorption of the free ions by clay minerals before analysis by ICP-MS. This simple method allows determining the distribution of DTPA chelates at concentration levels as low as a few 10 pmol/l. The transmetallation constants at ionic strength of 0.01 mol/l and room temperature are commensurable with those derived from published formation constants of the corresponding DTPA complexes. It could be proved that DTPA chelates of rare earth elements, Y and Cu are stable at least over 6 months. The pattern of the second-order rate constants shows a strong tetrad effect, which is not displayed by the pattern of transmetallation constants. Based on these results, the rate of transmetallation of Gd-DTPA under natural conditions is derived. The resultant process yields 10% turn-over of initial Gd-DTPA within two months, if Cu2+ concentrations are below 1 nmol/l. At higher concentrations, the turn-over increases with elapsed time. Equilibrium among REE and Y is expected only after tens of years. This makes Gd-DTPA a powerful tracer in hydrological studies.