Redox speciation of Tc in the aqueous phase was further confirmed by solvent extraction. A good agreement is obtained between the experimentally determined Tc redox distribution and thermodynamic calculations based on NEA-TDB (Nuclear Energy Agency, Thermochemical Database) and ionic strength corrections by SIT or Pitzer approaches. These observations indicate that experimental pH c and h values in buffered systems can be considered as reliable parameters to predict the redox behaviour of Tc in dilute to highly concentrated NaCl and MgCl 2 solutions. h of the system and aqueous concentration of Tc(IV) in equilibrium with TcO 2 ⋅ 1.6H 2 O(s) are strongly affected by elevated ionic strength, especially in the case of 4.5 M MgCl 2 solutions. In such concentrated brines and under alkaline conditions (pH c = pH max ∼ 9), kinetics play a relevant role and thermodynamic equilibrium for the system Tc(IV)(aq) ⇔ Tc(IV)(s) was not attained from oversaturation conditions within the timeframe of this study (395 days). Tc(VII) is reduced to Tc(IV) by magnetite, mackinawite and siderite suspensions at pH c = 8-9 in concentrated NaCl and MgCl 2 solutions. Sorption is very high in