The mechanisms for the reduction and uptake of Tc by magnetite (Fe₃O₄) and mackinawite (FeS) are investigated using X-ray absorption spectroscopy (XANES and EXAFS), in combination with thermodynamic calculations of the Tc/Fe systems and accurate characterization of the solution properties (pH_m, pe, [Tc]).

Redox behaviour of Tc(VII)/Tc(IV) was investigated in 0.1 M NaCl solutions containing different reducing agents in the pH range 2 to 13 at 22 ºC under inert Ar atmosphere. In several samples, the 1 × 10⁵ mol/dm³(M) initially added TcO₄^-was reduced to form a Tc(IV) oxide solid phase with low solubility. The observed Tc redox transformation processes are systematized according toE_h-pH conditions in solution, indicating that a borderline for the reduction of Tc(VII) to Tc(IV),TcO₄^-+ 3e^-+ 4H⁺⇔TcO₂·xH₂O(coll, hyd) + (2-x)H₂Oexists, independent of the reducing chemical system. This experimentally derived borderline is about 100 mV lower than the equilibrium line calculated from the reported standard redox potential of TcO₂· 1.6H₂O(s). This behaviour can be related to the existence of more soluble solid phase modifications,i.e.nanoparticulate Tc(IV) oxide species (TcO₂·xH₂O(coll, hyd)). The reaction kinetics likewise correlate to the redox potential measured in solution. Slow reduction of Tc(VII) to Tc(IV) was observed when the redox potential in the system was slightly below the above mentioned reduction borderline. Fast reduction was observed in the systems far below the borderline, but also in those systems containing Fe(II) solids, suggesting a specific surface mediated effect in the reduction process. EXAFS analysis on two magnetite samples indicate reduced Tc(IV) species which do not remain adsorbed at the reactive mineral surface and are incorporated in the magnetite structure.