Local environment of bismuth in iodine bearing aluminoborosilicate glasses: An X-ray Absorption Spectroscopic study at the Bi L3 edge
Abstract
Iodine-129 radioisotope produced from nuclear plant activity is problematic in the environment due to its long half-life and high mobility. Incorporation of iodine into highpressure glasses represents a possible solution for its immobilisation, however, the matrix formulation is still under construction. Addition of Bi2O3 to standard low activity waste glass composition appears to be beneficial for iodine incorporation. Notwithstanding, the exact relationship between iodine and bismuth remains to be determined.
We investigated the local environment for Bi (up to 16 mol.% Bi2O3) in I-free and I-bearing aluminoborosilicate glasses using X-ray Absorption Spectroscopy. We show that Bi exists as several redox state in the glass structure: mainly Bi 3+ and small proportion of Bi 5+ ; and that the apparent average Bi valence decreases from ~3.6 to ~3.0 as Bi₂O₃ increases from 1 to 16 mol.%, reflecting a smaller NaBiO₃-like (Bi⁵⁺) contribution at high Bi₂O₃ content. The Bi coordination number to nearest neighbour also decreases consistent with an increase in BiO3 3- clusters and witnessing a more disordered structure. On average, the Bi local environment appears independent of iodine incorporation suggesting that it does not intervene in the Bi first coordination shell. The decrease in Avg. redox state is possibly accompanied by a decrease in the available Non-Bridging Oxygens in the near vicinity of Bi atoms required for iodine incorporation. As such, addition of Bi2O3 acting as a network modifier is beneficial for iodine incorporation to a certain level of concentration and matrix formulation should take that aspect into consideration.
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BibTeX
@article{morizet2026local,
title = {{Local environment of bismuth in iodine bearing aluminoborosilicate glasses: An X-ray Absorption Spectroscopic study at the Bi L3 edge}},
author = {Yann Morizet and Gabin Haryouli and Clémentine Lapie and Sami Soudani and Emiliano Fonda and Nicolas Trcera and Jonathan Hamon and Michael Paris and Lionel Campayo},
journal = {Journal of Nuclear Materials},
year = {2026},
month = sep,
doi = {10.1016/j.jnucmat.2026.157050},
url = {https://hal.science/hal-05794481v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Local environment of bismuth in iodine bearing aluminoborosilicate glasses: An X-ray Absorption Spectroscopic study at the Bi L3 edge
AU - Yann Morizet
AU - Gabin Haryouli
AU - Clémentine Lapie
AU - Sami Soudani
AU - Emiliano Fonda
AU - Nicolas Trcera
AU - Jonathan Hamon
AU - Michael Paris
AU - Lionel Campayo
PY - 2026
DA - 2026/09/04
JO - Journal of Nuclear Materials
DO - 10.1016/j.jnucmat.2026.157050
UR - https://hal.science/hal-05794481v1
AB - Iodine-129 radioisotope produced from nuclear plant activity is problematic in the environment due to its long half-life and high mobility. Incorporation of iodine into highpressure glasses represents a possible solution for its immobilisation, however, the matrix formulation is still under construction. Addition of Bi2O3 to standard low activity waste glass composition appears to be beneficial for iodine incorporation. Notwithstanding, the exact relationship between iodine and bismuth remains to be determined. We investigated the local environment for Bi (up to 16 mol.% Bi2O3) in I-free and I-bearing aluminoborosilicate glasses using X-ray Absorption Spectroscopy. We show that Bi exists as several redox state in the glass structure: mainly Bi 3+ and small proportion of Bi 5+ ; and that the apparent average Bi valence decreases from ~3.6 to ~3.0 as Bi₂O₃ increases from 1 to 16 mol.%, reflecting a smaller NaBiO₃-like (Bi⁵⁺) contribution at high Bi₂O₃ content. The Bi coordination number to nearest neighbour also decreases consistent with an increase in BiO3 3- clusters and witnessing a more disordered structure. On average, the Bi local environment appears independent of iodine incorporation suggesting that it does not intervene in the Bi first coordination shell. The decrease in Avg. redox state is possibly accompanied by a decrease in the available Non-Bridging Oxygens in the near vicinity of Bi atoms required for iodine incorporation. As such, addition of Bi2O3 acting as a network modifier is beneficial for iodine incorporation to a certain level of concentration and matrix formulation should take that aspect into consideration.
SN - 0022-3115
SN - 1873-4820
ER -