Understanding the Mechanism of Cs Accumulation on Stainless Steel Suspended in Nuclear High-Level Liquid Waste.

In a nuclear facility, the surface of stainless steels (SS) was found to be contaminated during the processing of radioactive liquid waste. Their safe and secure disposal is highly challenging to the nuclear industry. If the fundamental property of steel corrosion could be evaluated, successful decontamination and effective decommissioning strategies could be planned. Although individual radionuclide contamination behavior on SS metal was studied, till date, SS contamination behavior under the exposure of high-level liquid waste (HLLW) was unexplored. In view of this, investigations were carried out to understand the nature of contamination in SS 304L alloy under the exposure of simulated HLLW (SHLLW). For understanding of radionuclide adsorption behavior on structural materials, scanning electron microscopy/energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy have been utilized for SS 304L. The solutions were analyzed using inductively coupled plasma optical emission spectroscopy to calculate the changes in the elemental composition of the solution and corrosion behavior of SS. The passivation of SS coupons was observed in the presence of HNO3 due to enrichment of Cr at the surface. The deposition of Cs and Mo was noticed, while SS coupons were exposed to SHLLW. At 3 M HNO3 and room temperature, the SS surface is mildly passivated by Cr enrichment by formation of a Cr oxide layer on the SS surface. However, the passive layer was not thick enough to attenuate the signal from the substrate below the passivated layer. Hence, Fe0 and Cr0 were also found along with Cr3+ and Fe3+ (in small quantity). When temperature was elevated to 70 °C, the SS surface was completely covered with the Cr oxide layer, and hence no Cr0 signal was observed. The small signal of Fe0 indicated that the signal from the substrate surface is present below the passive layer. During the passivation process, Cr diffused toward the passive layer, thereby producing a Cr-depleted layer below the passive layer (Cr0 signal was not seen). In the case of SHLLW at 70 °C, the surface was fully covered by Cr3+, Mo6+, and Cs+. Fe and Ni were not observed at all. This finding will help to design an effective corrosion inhibitor and suitable decontamination agent. In addition to that, this information was found to be useful in designing high-performance novel and modern age reactor materials with improved characteristics.

Mechanism unravelling for highly efficient and selective 99TcO4 - sequestration utilising crown ether based solvent system from nuclear liquid waste: experimental and computational investigations.

Selective and efficient separation of pertechnetate (TcO4 -) from nuclear waste is desirable for the safe and secure management of radioactive waste. Here, we have projected dibenzo-18-crown-6 ether (DB18C6) in a highly polar nitrobenzene medium for enhancing the removal efficiency of 99Tc from reprocessing plant low level waste (LLW). An effort was made to determine the stoichiometry of metal-ligand complex by slope ratio method, revealing that one ligand (DB18C6) binds with one TcO4 - moiety. Optimum ligand concentration for 99Tc extraction was evaluated. Relevant interference of the anions was studied systematically. The effect of solution pH was analysed on the extraction efficiency of 99Tc. A kinetic study was carried out for maximum extraction of metal ions. A quantitative stripping study was also achieved for metal ions with a suitable stripping solution. After evaluation of all essential parameters, selectivity and feasibility studies were finally carried out with actual low level reprocessing plant waste to demonstrate a laboratory scale process for effective separation of TcO4 - ions. Density functional theory (DFT) calculations were carried out to understand the nature of the complexation of TcO4 - ion with DB18C6 in different solvents systems and to elucidate the key aspect behind ionic selectivity and enhanced the 99Tc extraction efficiency of DB18C6 in the studied diluent systems. The ΔE and ΔG values for different modeled complexation reactions were evaluated systematically. From the calculated free energy of complexation of TcO4 - with DB18C6, it was observed that the consideration of explicit solvent plays a vital role in predicting the experimental selectivity.

Correction: Mechanism unravelling for highly efficient and selective 99TcO4 - sequestration utilising crown ether based solvent system from nuclear liquid waste: experimental and computational investigations.

[This corrects the article DOI: 10.1039/D1RA07738D.].

Metal-organic frameworks as superior porous adsorbents for radionuclide sequestration: Current status and perspectives.

Efficient separation of hazardous radionuclides from radioactive waste remains a challenge to the global acceptance of nuclear power due to complex nature of the waste, high radiotoxicities and presence of large number of interfering elements. Sorption of radioactive elements from liquid phase, gas phase or their solid particulates on various synthetic organic, inorganic or biological sorbents is looked as one of the options for their remediation. In this context, highly porous materials, termed as metal-organic frameworks (MOFs), have shown promise for efficient capturing of various types of radioactive elements. Major advantages that have been advocated for the application of MOFs in radionuclide sorption are their excellent chemical stability, and their large surface area due to abundant functional groups, and porosity. In this review, recent developments on the application of MOFs for radionuclide sequestration are briefly discussed. Focus has been devoted to address the separation of few crucial radioactive elements such as Th, U, Tc, Re, Se, Sr and Cs from aqueous solutions, which are important for liquid radioactive waste management. Apart from these radioactive metal ions, removal of radionuclide bearing gases such as I2, Xe, and Kr are also discussed. Aspects related to the interaction of MOFs with the radionuclides are also discussed. Finally, a perspective for comprehensive investigation of MOFs for their applications in radioactive waste management has been outlined.

Achieving highly efficient and selective cesium extraction using 1,3-di-octyloxycalix[4]arene-crown-6 in n-octanol based solvent system: experimental and DFT investigation.

Due to the long half-life of 137Cs (t 1/2 ∼ 30 years), the selective extraction of cesium (Cs) from high level liquid waste is of paramount importance in the back end of the nuclear fuel cycle to avoid long term surveillance of high radiotoxic waste. As 1,3-di-octyloxycalix[4]arene-crown-6 (CC6) is suggested to be a promising candidate for selective Cs extraction, the improvement in the Cs extraction efficiency by CC6 has been investigated through the optimization of the effect of dielectric media on the extraction process. The effects of the feed acid (HNO3, HCl, and HClO4) and the composition of the diluents for the ligand in the organic phase on the extraction efficiency of Cs have been investigated systematically. In 100% n-octanol medium, Cs is found to form a 1 : 1 ion-pair complex with CC6 (0.03 M) providing a very high distribution ratio of D Cs ∼ 22, suggesting n-octanol as the most suitable diluent for Cs extraction. No significant interference of other relevant cations such as Na, Mg and Sr was observed on the D Cs value in the optimized solvent system. Density functional theory (DFT) based calculations have been carried out to elucidate the reason of ionic selectivity and enhanced Cs extraction efficiency of CC6 in the studied diluent systems. In addition to the ionic size-based selectivity of the crown-6 cavity, the polarity of the organic solvent system, the hydration energy of the ion, and the relative reorganization of CC6 upon complexation with Cs are understood to have roles in achieving the enhanced efficiency for the extraction of Cs by the CC6 extractant in nitrobenzene medium.