New Insights into 99Tc(VII) Removal by Pyrite: A Spectroscopic Approach

99Tc­(VII) uptake by synthetic pure pyrite at 21 °C was studied in a wide pH range from 3.50 to 10.50 using batch experiments combined with scanning electron microscopy, X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and Raman microscopy. We found that pyrite removes Tc quantitatively from solution (log K d = 5.0 ± 0.1) within 1 day at pH ≥ 5.50 ± 0.08. At pH < 5.50 ± 0.08, the uptake process is slower, leading to 98% Tc removal (log K d = 4.5 ± 0.1) after 35 days. The slower Tc uptake was explained by higher pyrite solubility under acidic conditions. After 2 months in contact with oxygen at pH 6.00 ± 0.07 and 10.00 ± 0.04, Tc was neither reoxidized nor redissolved. XAS showed that the uptake mechanism involves the reduction from Tc­(VII) to Tc­(IV) and subsequent inner-sphere complexation of Tc­(IV)–Tc­(IV) dimers onto a Fe oxide like hematite at pH 6.00 ± 0.07, and Tc­(IV) incorporation into magnetite via Fe­(III) substitution at pH 10.00 ± 0.04. Calculations of Fe speciation under the experimental conditions predict the formation of hematite at pH < 7.50 and magnetite at pH > 7.50, explaining the formation of the two different Tc species depending on the pH. XPS spectra showed the formation of TcSx at pH 10.00 ± 0.04, being a small fraction of a surface complex, potentially a transient phase in the total redox process.