A "Two-Step" Electrochemical Approach for Recovery of Plutonium and Uranium from Aqueous Acidic Waste Solutions.

Chemical quality control of nuclear fuel, particularly the determination of Pu and U contents by chemical methods, results in analytical acidic aqueous waste solutions from which Pu and U must be recovered efficiently for the remediation of radioactive wastes. Reported methods involve several complicated steps requiring addition of chemical oxidants/reductants for valence adjustments and generation of secondary wastes, thereby making the recovery process cumbersome. Herein, we report a novel two-step electrochemical approach for Pu and U recovery from acidic aqueous waste solutions containing different metallic impurities (Fe, Cr, Mn, Cd, Al, Ni, Co, Zn, and Mg) by bulk electrolysis using a Pt gauze electrode. Pu and U are recovered from these waste solutions in a two-step process: (i) bulk electrolysis of the mixed solution at a constant potential of 0.1 V vs Ag/AgCl/3 M KCl that results in the reduction of PuO22+ to Pu3+ followed by the precipitation of Pu3+ as K2(K0.5Pu0.5)(SO4)2, which is then filtered and separated and (ii) the filtrate solution is again subjected to bulk electrolysis at a constant potential of -0.35 V vs Ag/AgCl/3 M KCl resulting in the reduction of UO22+ to U4+. The U4+ is then precipitated as K2(K0.67U0.33)(SO4)2, which is filtered and separated, leading to a Pu- and U-free aqueous acidic waste solutions. Biamperometry shows that 97.8% and 99.1% recovery of Pu and U, respectively, is possible, and emission spectrometry confirms the purity of K2(K0.5Pu0.5)(SO4)2 and K2(K0.67U0.33)(SO4)2. Because of its operational simplicity, potential for remote handling, and excellent extraction efficiency, the present methodology can easily replace traditional methods for the recovery of Pu and U from acidic aqueous waste solutions.

Poly(3,4-ethylenedioxythiophene)-Poly(styrenesulfonate)-Coated Glassy-Carbon Electrode for Simultaneous Voltammetric Determination of Uranium and Plutonium in Fast-Breeder-Test-Reactor Fuel.

Uranium (U) and plutonium (Pu) contents in nuclear materials must be maintained to a definite level in order to get the desired performance of the fuel inside the reactor. Therefore, high accuracy and precision is an essential criterion for the determination of U and Pu. We already reported the voltammetric determination of Pu in the presence of U in fast-breeder-test-reactor (FBTR) fuel samples, but interfacial, coupled chemical reactions between U(IV) and Pu(IV) enhance the peak-current density of U(VI) reduction and thus make voltammetry unsuitable for the quantitative determination of U in the presence of Pu. Thus, developing a voltammetric method for the simultaneous determination of U and Pu is highly challenging. Herein, we report the simultaneous voltammetric determination of U and Pu in 1 M sulfuric acid (H2SO4) on a poly(3,4-ethylenedioxythiophene) (PEDOT)-poly(styrenesulfonate) (PSS)-modified glassy-carbon (GC) electrode (PEDOT-PSS/GC). The modified electrode shows enhanced performance compared with bare GC electrodes. The peak-current density for U(VI) reduction is enhanced in the presence of Pu(IV), but it attains saturation when [Pu]/[U] in solution is maintained ≥2. Hence, under these circumstances, the variation of Pu concentration no longer influences the U(VI)-reduction peak, and thus the quantitative determination of U in the presence of Pu is possible. No interference is observed from commonly encountered impurities present in FBTR fuel samples. This method shows accuracy and precision comparable to those of the biamperometry method. High robustness, fast analysis, simultaneous determination, reduced radiation exposure to the analyst, and ease of recovery of U and Pu from analytical waste makes it a suitable candidate to substitute the presently applied biamperometry method.

Understanding the excited state dynamics and redox behavior of highly luminescent and electrochemically active Eu(III)-DES complex.

Deep eutectic solvents (DES) are considered a novel class of environmentally benign molecular solvents that are considered as potential solvents for nuclear fuel reprocessing, material recycling, and many other technological applications in both research and industry. However, there is a complete dearth of understanding pertaining to the behavior of metal ions in DES. Herein, we have investigated the speciation, complexation behavior, photochemistry, and redox properties and tried to obtain insight into the chemical aspects of the europium ion in DES (synthesized from heptyltriphenylphosphonium bromide and decanoic acid). The same has been probed using time-resolved photoluminescence (TRPL), cyclic voltammetry (CV), synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) calculations. TRPL indicated the stabilization of europium in the +3 oxidation state, favoring the potential of the Eu(III)-DES complex to emit red light under near UV excitation and the existence of inefficient energy transfer between DES and Eu3+. EXAFS analysis revealed the presence of Eu-O and Eu-Br, which represent the local surroundings of Eu3+ in the Eu(III)-DES complex. TRPL measurement has also suggested two distinct local environments of europium ions in the complex. DFT calculations supported the EXAFS findings, confirming that the Eu(III)-DES structure involves not only the oxygen atom of decanoic acid but also the oxygen atoms from the nitrate ions, contributing to the local coordination of Eu(III). Electrochemical studies demonstrated that the redox reaction of Eu(III)/Eu(II) in DES displays quasi-reversible behavior. The reaction rate was observed to increase with higher temperatures. The findings of this study can contribute to the understanding of the fundamental properties and potential applications of this luminescent and electrochemically active complex and pave the way for further studies and the development of novel materials with enhanced luminescent and electrochemical properties.

Electrochemical recovery of plutonium from aqueous carbonate waste solutions.

Recovery of plutonium from aqueous carbonate waste solutions generated during the reprocessing of spent nuclear fuel is a key concern for sustainable nuclear energy programmes and the remediation of radioactive waste. Reported methods proceed through secondary waste generation caused by acidification of carbonate waste and make the recovery process cumbersome. Herein, we report a simple method for the recovery of Pu as solid PuO2 powder from carbonate waste solution in a two-step process. (i) Pu was selectively electrochemically precipitated as plutonium-hydroxide in the presence of interfering U, Th, Ru, Zr, Nb, Cs and the degradation products of tri-butyl phosphate by bulk electrolysis at -0.9 V using a Pt gauze electrode and (ii) the precipitate was annealed at 973 K for conversion to pure PuO2 powder. The present approach is simple, avoids the generation of secondary waste and reduces the exposure of working personnel to radiation.

Influence of sulfuric acid concentration in the simultaneous voltammetric determination of uranium and plutonium in nuclear fuels.

Interfacial coupled chemical reaction between U(iv) (formed at the electrode surface) and Pu(iv) (diffuses from the bulk towards the electrode) regenerates U(vi) at the electrode-solution interface and causes enhancement in the U(vi) reduction current, thus creating problems in the simultaneous voltammetric determination of U and Pu. Despite such interference between U(iv) and Pu(iv), the simultaneous voltammetric determination of U and Pu in FBTR Mark-1 fuel samples in sulfuric acid (1 M H2SO4) on a poly(3,4-ethylenedioxythiophene) (PEDOT)-poly(styrenesulfonate) (PSS)-modified glassy-carbon (GC) electrode (PEDOT-PSS/GC) has been reported. However, the reported method is applicable only for FBTR mark-1 fuel samples, in which the ratio [Pu]/[U] > 2 is always maintained. For nuclear samples having [Pu]/[U] < 2 (e.g., PFBR fuel), the simultaneous voltammetric determination of U and Pu is extremely challenging. Herein, we report a modified version of the earlier method for the simultaneous determination of U and Pu in nuclear samples ((U, Pu)C and (U, Pu)O2), irrespective of the [Pu]/[U] ratio. The effect of acidity (H2SO4 conc.) on the coupled chemical reaction between U(iv) and Pu(iv) was examined. It was observed that an increase in the acidity of H2SO4 minimized the coupled chemical reaction, and at 5 M H2SO4, change in the Pu(iv) concentration did not have any effect on the U(vi) reduction current. The coupled chemical reaction between U(iv) and Pu(iv) ceased at 5 M H2SO4 and hence, the simultaneous voltammetric determination of U and Pu was possible on PEDOT-PSS/GC, irrespective of the [Pu]/[U] ratio in 5 M H2SO4. The method was applied for both (U, Pu)O2 (PFBR) and (U, Pu)C (FBTR) samples and was compared with the well-established biamperometric method. The present method shows accuracy and precision comparable to biamperometry and did not show any interference from the commonly encountered impurities in nuclear samples. Thus, both FBTR and PFBR nuclear fuels having different [Pu]/[U] ratios can be analyzed by the present approach and it is a strong competitor to replace the well-established biamperometric method for routine sample analysis.

Remarkably enhanced direct dissolution of plutonium oxide in task-specific ionic liquid: insights from electrochemical and theoretical investigations.

The present work envisages an approach for direct dissolution of PuO2 in a task-specific ionic liquid (TSIL). An attractive possibility to electrodeposit plutonium from the mixture of TSIL and PuO2 has been explored further. The carboxyl functional group attached to the TSIL plays a key role in facilitating the dissolution of plutonium ions.