Technetium Complexation with Multidentate Carboxylate-Containing Ligands: Trends in Redox and Solubility Phenomena.

The chemistry of technetium ( t _1/2 ( ⁹⁹ Tc) = 2.11 × 10 ⁵ years) is of particular importance in the context of nuclear waste disposal and historic contaminated sites. Polycarboxylate ligands may be present in some sites and are potentially capable of strong complexing interactions, thus increasing the solubility and mobility of ⁹⁹ Tc under environmentally relevant conditions. This work aimed to determine the impact of five organic complexing ligands [L = oxalate, phthalate, citrate, nitrilotriacetate (NTA), and ethylenediaminetetraacetate (EDTA)] under anoxic, alkaline conditions (pH ≈ 9-13) on the solubility of technetium. X-ray absorption spectroscopy confirmed that TcO ₂ (am,hyd) remained the solubility-controlling solid phase in undersaturation solubility experiments. Ligands with maximum coordination numbers (CN) ≥ 3 (EDTA, NTA, and citrate) exhibited an increase in solubility from pH 9 to 11, while ligands with CN ≤ 2 (oxalate and phthalate) at all investigated pH and CN ≥ 3 at pH ≈ 13 were outcompeted by hydrolysis reactions. Though most available thermodynamic values were determined under acidic conditions, these models satisfactorily explained high-pH undersaturation solubility of technetium for citrate and NTA, whereas experimental data for Tc(IV)-EDTA were highly overestimated. This work illustrates the predominance of hydrolysis under hyperalkaline conditions and provides experimental support for existing thermodynamic models of Tc-L except Tc-EDTA, which requires further research regarding aqueous speciation and solubility.