Impact of the degradation leachate of the polyacrylonitrile-based material UP2W on the retention of Ni(II), Eu(III) and Pu(IV) by cement

The uptake of $^{63}$Ni(II), $^{152}$Eu(III) and $^{242}$Pu(IV) by hardened cement paste (HCP, CEM I) in the degradation stage II (pH ≈ 12.5, [Ca] ≈ 0.02 M) was investigated in the presence of a degradation leachate of UP2W, a polyacrylonitrile-based (PAN) material used as a filter aid in nuclear power plants. The degradation leachate with a concentration of dissolved organic carbon of ∼40 ppm was obtained from the degradation of UP2W in portlandite-buffered solutions for ca. 1100 days. Redox conditions in the Pu systems were buffered with hydroquinone, which defines mildly reducing conditions (pe + pH ≈ 10) where Pu(IV) is the predominant oxidation state. The degradation leachate investigated in this work is moderately sorbed by cement, with distribution ratios (R$_d$) of (0.35 ± 0.15) m$^3$ kg$^{−1}$. These values are 30 to 100 times greater than distribution ratios previously reported for proxy ligands of PAN degradation products, i.e., glutaric acid, α-hydroxyisobutyric acid and 3-hydroxybutyric acid. The presence of the degradation leachate induces a moderate decrease in the uptake of $^{63}$Ni(II), $^{152}$Eu(III) and $^{242}$Pu(IV) by cement, as compared to the sorption in the presence of the proxy ligands. ... mehrNevertheless, retention in the presence of the degradation leachate remains high for all investigated radionuclides, with Rd($^{63}$Ni(II)) ≈ 2 m$^3$ kg$^{−1}$, Rd($^{152}$Eu(III)) ≈ 100 m$^3$ kg$^{−1}$ and Rd($^{242}$Pu(IV)) ≈ 30 m$^3$ kg$^{−1}$. These observations possibly reflect that the multiple functionalities (–COOH, –OH, amide groups) expected in the macromolecules (10–15 kDa) present in the degradation leachate, can offer further binding/chelating capabilities compared to the small organic proxy ligands with at most bidentate binding.