The mechanisms for the reduction and uptake of Tc by magnetite (FeO) 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, pe, [Tc]). Batch sorption experiments were performed under strictly anoxic conditions using freshly prepared magnetite and mackinawite in 0.1 M NaCl solutions with varying initial Tc(vii) concentrations (2 × 10 and 2 × 10 M) and Tc loadings (400-900 ppm). XANES confirms the complete reduction of Tc(vii) to Tc(iv) in all investigated systems, as predicted from experimental (pH + pe) measurements and thermodynamic calculations. Two Tc endmember species are identified by EXAFS in the magnetite system, Tc substituting for Fe in the magnetite structure and Tc-Tc dimers sorbed to the magnetite {111} faces through a triple bond. The sorption endmember is favoured at higher [Tc], whereas incorporation prevails at low [Tc] and less alkaline pH conditions. The key role of pH in the uptake mechanism is interpreted in terms of magnetite solubility, with higher [Fe] and greater recrystallization rates occurring at lower pH values. A TcS-like phase is predominant in all investigated mackinawite systems, although the contribution of up to 20% of TcO·xHO(s) (likely as surface precipitate) is observed for the highest investigated loadings (900 ppm). These results provide key inputs for an accurate mechanistic interpretation of the Tc uptake by magnetite and mackinawite, so far controversially discussed in the literature, and represent a highly relevant contribution to the investigation of Tc retention processes in the context of nuclear waste disposal.

A novel procedure has been developed for the measurement of (143)Nd/(144)Nd isotope ratio in various uranium-bearing materials, such as uranium ores and ore concentrates (UOC) in order to evaluate the usefulness and applicability of variations of (143)Nd/(144)Nd isotope ratio for provenance assessment in nuclear forensics. Neodymium was separated and pre-concentrated by extraction chromatography and then the isotope ratios were measured by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The method was validated by the measurement of standard reference materials (La Jolla, JB-2 and BCR-2) and the applicability of the procedure was demonstrated by the analysis of uranium samples of world-wide origin. The investigated samples show distinct (143)Nd/(144)Nd ratio depending on the ore type, deposit age and Sm/Nd ratio. Together with other characteristics of the material in question, the Nd isotope ratio is a promising signature for nuclear forensics and suggests being indicative of the source material, the uranium ore.

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We present the first systematic investigation of Tc(iv) solubility, hydrolysis and speciation in dilute to concentrated NaCl, MgCl2 and CaCl2 systems, and comprehensive thermodynamic and activity models for the system Tc(4+)-H(+)-Na(+)-Mg(2+)-Ca(2+)-OH(-)-Cl(-)-H2O using both SIT and Pitzer approaches. The results are advancing the fundamental scientific understanding of Tc(iv) solution chemistry and are highly relevant in the applied context of nuclear waste disposal. The solubility of Tc(iv) was investigated in carbonate-free NaCl-NaOH (0.1-5.0 M), MgCl2 (0.25-4.5 M) and CaCl2 (0.25-4.5 M) solutions within 2 ≤ pHm≤ 14.5. Undersaturation solubility experiments were performed under an Ar atmosphere at T = 22 ± 2 °C. Strongly reducing conditions (pe + pHm≤ 2) were imposed with Na2S2O4, SnCl2 and Fe powder to stabilize technetium in the +IV redox state. The predominance of Tc(iv) in the aqueous phase was confirmed by solvent extraction and XANES/EXAFS spectroscopy. Solid phase characterization was accomplished after attaining thermodynamic equilibrium using XRD, SEM-EDS, XANES/EXAFS, TG-DTA and quantitative chemical analysis, and indicated that TcO2·0.6H2O(s) exerts solubility-control in all evaluated systems. The definition of the polyatomic Tc3O5(2+) species instead of TcO(2+) is favoured under acidic conditions, consistently with slope analysis (mTcvs. pHm) of the solubility data gained in this work and spectroscopic evidence previously reported in the literature. The additional formation of Tc(iv)-OH/O-Cl aqueous species in concentrated chloride media ([Cl(-)] = 9 M) and pHm≤ 4 is suggested by solubility and EXAFS data. The pH-independent behaviour of the solubility observed under weakly acidic to weakly alkaline pHm conditions can be explained with the equilibrium reaction TcO2·0.6H2O(s) + 0.4H2O(l) ⇔ TcO(OH)2(aq). Solubility data determined in dilute NaCl systems with pHm≥ 11 follow a well-defined slope of +1, consistent with the predominance of TcO(OH)3(-) previously selected by NEA-TDB. In concentrated MgCl2 and CaCl2 solutions with pHm≥ 8, the formation of the ternary Mg3[TcO(OH)5](3+) and Ca3[TcO(OH)5](3+) species is proposed based on the slope analysis of the solubility data, model calculations and previous observations for analogous An(iv) and Zr(iv) systems. The formation and stability of these hitherto unknown Tc(iv) species are supported by DFT calculations. Based on the newly generated experimental data and previous spectroscopic observations, new comprehensive chemical, thermodynamic and activity models (SIT, Pitzer) for these systems are derived.

The biosorption of Ce(III) from aqueous solution by citric acid-modified Pinus brutia leaf powder was studied in a batch system as a function of initial pH, temperature, initial concentration of adsorbate, and contact time. Central composite design method was used in the experiments. Thermodynamic parameters such as standard enthalpy (DH 0 ), entropy (DS 0 ), and free energy (DG 0 ) were calculated, and the results indicated that biosorption was exothermic. The biosorption of Ce(III) on modified Pinus brutia leaf powder was investigated by Freundlich, Langmuir, and Dubinin-Radushkevich (D-R) isotherms. The results show that Ce(III) adsorption can be explained by Langmuir isotherm model, and monolayer capacity was found as 62.1 mg/g. The results suggested that the modification process enhances the biosorption capacity of the adsorbent, and modified Pinus brutia leaf powder may find promising applications for the recovery of Ce(III) from aqueous effluents.

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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

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