Rizaal Muhammad, Nakajima Kunihisa
Nuclear Science and Engineering Center, Japan Atomic Energy Agency, 2-4 Shirane, Shirakata, Tokai-mura, Naka-gun, Ibaraki, 319-1195, Japan.
Chemosphere. 2024 Sep;363:142870. doi: 10.1016/j.chemosphere.2024.142870. Epub 2024 Jul 15.
Retention or trapping of cesium, one of the radiologically important fission products, in the nuclear reactor becomes a great concern as the occurrence may affect radioactivity in the long term or its environmental fate. Herein the chemical compound of cesium that had been largely trapped on the nuclear reactor structural material of (calcium silicate) thermal insulator in a simulated nuclear accident condition was investigated. A combined pre- and post-water dissolution analysis through infrared (IR) spectroscopy and optical emission spectroscopy (OES) was explored to resolve the characterization difficulty encountered in conventional X-ray diffraction analysis reported in the previous works. This method allowed us to identify for the first time the related large amount of water-soluble cesium in the calcium silicate material after a high-temperature chemical reaction as cesium metasilicate (CsSiO). It was evidenced by similar vibrational characteristics of the material to that in the synthesized CsSiO as well as based on the dissolved Cs and Si in the leaching water having a molar ratio of 2.16 ± 0.33. The corresponding 79-98% of the retained cesium in calcium silicate materials in the case study of 700 and 800 °C reactions was of this compound, emphasizing its significance once formed. Thermodynamic considerations further corroborated the higher stability of CsSiO in the cesium-calcium silicate reaction than other cesium silicates such as CsSiO, CsSiO, or CsSiO. This clearly poses a high environmental risk due to the volatility of cesium metasilicate as it may spread out further through the water leak path from a damaged nuclear reactor.
作为具有重要放射学意义的裂变产物之一,铯在核反应堆中的滞留或捕获成为一个重大问题,因为这种情况可能会长期影响放射性或其环境归宿。本文研究了在模拟核事故条件下,大量滞留在(硅酸钙)隔热材料这种核反应堆结构材料上的铯的化合物。为了解决先前工作中报道的传统X射线衍射分析所遇到的表征困难,探索了一种通过红外(IR)光谱和光发射光谱(OES)进行水溶解前后联合分析的方法。该方法使我们首次确定,在高温化学反应后,硅酸钙材料中存在大量与偏硅酸铯(CsSiO₃)相关的水溶性铯。这是通过该材料与合成的CsSiO₃具有相似的振动特性以及基于浸出水中溶解的Cs和Si的摩尔比为2.16±0.33来证明的。在700和800℃反应的案例研究中,硅酸钙材料中相应79 - 98%的滞留铯是这种化合物,这突出了其一旦形成后的重要性。热力学考量进一步证实,在铯 - 硅酸钙反应中,CsSiO₃比其他硅酸铯如Cs₂SiO₄、Cs₄SiO₄或Cs₃Si₂O₅具有更高的稳定性。由于偏硅酸铯的挥发性,这显然带来了很高的环境风险,因为它可能会通过受损核反应堆的漏水路径进一步扩散。