The β-emitting 99 Tc isotope is a high-yield fission product in 235 U and 239 Pu nuclear reactors, raising special concern in nuclear waste management due to its long half-life and the high mobility of pertechnetate (TcO4 - ). Under the conditions of deep nuclear waste repositories, Tc is retained through biotic and abiotic reduction of TcO4 - to compounds like amorphous TcO2 ⋅ xH2 O precipitates. It is generally accepted that these precipitates have linear (Tc(μ-O)2 (H2 O)2 )n chains, with trans H2 O. Although corresponding Tc-Tc and Tc-O distances have been obtained from extended X-ray absorption fine structure (EXAFS) spectroscopy, this structure is largely based on analogy with other compounds. Here, we combine density-functional theory with EXAFS measurements of fresh and aged samples to show that, instead, TcO2 ⋅ xH2 O forms zigzag chains that undergo a slow aging process whereby they combine to form longer chains and, later, a tridimensional structure that might lead to a new TcO2 polymorph.
Keywords: EXAFS spectroscopy; chain structures; density functional calculations; nuclear waste management; technetium.
© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.