Laser Ablation Saturated Absorption Spectroscopy (LA-SAS) for In Situ Detection of Neodymium Isotopes.

This study introduces a novel optical system integrating laser ablation with saturated absorption spectroscopy (LA-SAS) for the detection of neodymium isotopes, crucial for the characterization process in nuclear forensics. Conventional methods for isotope analysis have encountered challenges, such as the inability to perform on-site detection or difficulty in distinguishing minor isotope differences. The LA-SAS system overcomes these limitations by combining pulsed laser for ablation and counter-propagated diode laser for saturated absorption, enabling preparation-free detection with enhanced spectral resolution. The analytical capability was demonstrated through the successful detection of seven neodymium isotopes (142Nd, 143Nd, 144Nd, 145Nd, 146Nd, 148Nd, and 150Nd) with a line width narrowed to 0.1 pm, significantly improving upon the resolution limit of conventional LA-based methods. In addition, quantitative analysis of isotope abundance was facilitated by evaluating the signals from saturated absorption spectra. Special attention was given to the hyperfine structure of odd isotopes, which was resolved by multiple fitting in spectra, thereby refining the accuracy of isotope quantification up to an average bias of 0.45%. The established LA-SAS system offers on-site detection capability based on LA, and also the high resolution from SAS, making it a promising method for in situ nuclear forensics. Consequently, the study enhances the academic understanding of neodymium isotopes and underscores the potential of LA-SAS in fields requiring detailed isotopic information.

Compensating isotope effect on molecular emission of hydroxyl and imidogen isotopologues in laser-induced plasma.

BACKGROUND: The molecular isotopologues in laser-induced plasma exhibit riddling emission behaviors in terms of wavelength, intensity, and temporal evolution of spectra due to the isotope effect. Although this phenomenon introduces uncertainty to isotope analyses based on molecular spectra, its underlying mechanism remains undisclosed. RESULTS: In this study, laser-induced breakdown spectroscopy (LIBS) is employed to identify the emission behavior of hydrogen, oxygen, and nitrogen isotopologues in a plasma plume. The goal is to discern the details of the isotope effect and mitigate resulting uncertainty. The molecular emissions of hydroxyl (OH) and imidogen (NH) were measured from plasma ablated on isotopically enriched water samples. Time-resolved detection clearly reveals distinct isotopic disparities in intensity variation and optimum gate delay, which were attributed to plasma thermo-hydrodynamics. Lighter isotopologues exhibit earlier and faster associations than their heavier counterparts due to their fast reaction rates and expansion velocities. The extent of the isotope effect hinged on plasma characteristics governed by measurement conditions. Consequently, comparing spectral intensity between molecular isotopologues cannot directly indicate the nominal isotope abundance of the sample. To address it, a compensation strategy has been devised, quantifying isotope effects through parameters like the slope and optimum delay of time-resolved detection. The approach successfully predicts nominal isotope abundance using compensated intensity ratios, with an absolute bias of less than 3 %. SIGNIFICANCE: This study not only offered fundamental insights into the isotope effect in laser-induced plasma but also proposed an alternative method for isotope quantification that circumvents complicated calibration processes.

Visible-NIR absorption spectroscopy study of the formation of ternary plutonyl(VI) carbonate complexes.

We present the first experimental evidence for the ternary complexation of calcium and magnesium ions with plutonyl(vi)tricarbonate species in carbonate-containing aqueous solutions using visible-NIR spectrophotometric titration. Prior to studying the ternary plutonyl(vi) carbonate complexation, visible-NIR absorption spectral information of PuO2(CO3)22- and PuO2(CO3)34- was successfully obtained. PuO2(CO3)22- has a prominent peak at 853 nm and its molar absorptivity was determined to be ε853, PuO2(CO3)22- = 49.0 ± 4.2 M-1·cm-1. The spectrophotometric titration results by adding calcium or magnesium to the plutonyl(vi) carbonate system consisting of PuO2(CO3)22- and PuO2(CO3)34- indicate the formation of CaPuO2(CO3)32- and MgPuO2(CO3)32- complexes and provide the formation constants at 0.1 M H/NaClO4 for MPuO2(CO3)32- from PuO2(CO3)34-, log K = 4.33 ± 0.50 and 2.58 ± 0.18 for M = Ca2+ and Mg2+, respectively. In addition, the formation constants of CaPuO2(CO3)32- and MgPuO2(CO3)32- from PuO2(CO3)34- at infinite dilution (log K°) were proposed to be 6.05 ± 0.50 and 4.29 ± 0.18, respectively, based on the correction of ionic strength using the Davies equation. The absorption spectrum of the ternary plutonyl(vi) complexes of CaPuO2(CO3)32- is similar to that of PuO2(CO3)34- with the exception of a characteristic absorption peak at 808 nm (ε808, CaPuO2(CO3)32- = 42.9 ± 1.6 M-1·cm-1). According to the calculated aqueous plutonyl(vi) speciation including the ternary plutonyl(vi) complexes, CaPuO2(CO3)32- is considered the dominant Pu(vi) species under environmental conditions, and plutonyl(vi) may be more mobile than expected in previous assessments.

Efficient removal of iodide anion from aqueous solution with recyclable core-shell magnetic Fe3O4@Mg/Al layered double hydroxide (LDH).

Magnetic Mg/Al layered double hydroxides (LDH) with three cationic ratios (Mg/Al = 2:1, 3:1, and 4:1) were successfully synthesized and utilized for the first time in an iodide adsorption study. The effects of the Mg/Al ratio of LDH on iodide adsorption were investigated, and physicochemical properties of synthetic LDHs depending on Mg/Al ratio were confirmed by XRD, TEM, ICP-OES, VSM, Zeta-potential, and BET analyses. The ferrimagnetic property was well preserved even after a coating of LDH on magnetite irrespective of the Mg/Al ratio. Among the three Mg/Al ratios, the calcined Fe3O4@4:1 Mg/Al LDH exhibited excellent performance for iodide removal with 105.04 mg/g of the maximum iodide adsorption capacity due to its wide interlayer spacing and largest BET surface area. In the presence of competing carbonate anions, the Fe3O4@4:1 LDH showed removal rate of >80% at a dosage of over 3 g/L solid to liquid ratio. The recyclability test of Fe3O4@4:1 LDH showed that the removal performance for iodide is maintained at >80% even during the first to the fourth cycles. These results demonstrated that the magnetic Mg/Al LDH adsorbent can be effectively utilized for remediation of radioactive iodide anions with high efficiency and economics.

Complexation of UO2(CO3)34- with Mg2+ at varying temperatures and its effect on U(vi) speciation in groundwater and seawater.

The ternary alkaline earth metal uranyl tricarbonate complexes, MnUO2(CO3)32n-4 (M = Mg and Ca), have been considered to be the major U(vi) species contributing to uranium mobility in natural water. Although MgUO2(CO3)32- can account for a substantial portion of U(vi) in a Mg2+-rich aqueous system and most processes regarding uranium are subjected to variable temperatures, chemical thermodynamic data for the prediction of the formation of MgUO2(CO3)32- at variable temperatures are still unknown. To fill the knowledge gap in the current chemical thermodynamic database, ultraviolet/visible (UV/Vis) absorption spectroscopy was employed to determine the formation constants (log K') of MgUO2(CO3)32- at varying temperatures of 10-85 °C in 0.5 mol kg-1 NaCl. The formation constants at infinite dilution, log K°, were obtained with specific ion interaction theory (SIT), and an increasing tendency of log K° with temperature was observed. Using calorimetric titration, the endothermic molar enthalpy of reaction (ΔrHm) of Mg2+ complexation with UO2(CO3)34- was determined at 25 °C. According to the chemical thermodynamic data obtained in this work, approximation models for the prediction of the temperature-dependent formation constant at a given temperature were examined and the constant enthalpy approximation with modification to the isoelectric reaction showed a satisfactory agreement with our experimental results. Finally, the effects of temperature on U(vi) speciation in Mg2+-rich groundwater and U(vi) extraction from seawater by amidoxime derivatives were examined. For the first time, this work provides important chemical thermodynamic data of MgUO2(CO3)32n-4 to assess the impact of temperature on U(vi) behaviour in groundwater and seawater.

Formation of CaUO2(CO3)32- and Ca2UO2(CO3)3(aq) complexes at variable temperatures (10-70 °C).

The ternary complexation of calcium uranyl tricarbonate species, CaUO2(CO3)32- and Ca2UO2(CO3)3(aq), which are the predominant U(vi) complexes in groundwater and seawater, was investigated at variable temperatures from 10 to 70 °C. Time-resolved laser fluorescence spectroscopy (TRLFS), calcium ion-selective electrode potentiometry, and ultraviolet/visible (UV/Vis) absorption spectroscopy were complementarily employed to determine the formation constants (log Kx13, x = 1 and 2 for mono- and dicalcium complexes, respectively). at infinite dilution (zero ionic strength) was determined by correction using specific ion interaction theory (SIT), and an increasing tendency of with temperature was observed. In addition, the molar enthalpy of complexation (ΔrHm) was measured by calorimetry at 25 °C. Based on thermodynamic data obtained in this work, the approximation models were examined for the prediction of the temperature effect on the complexation, and the constant enthalpy approximation with the chemical complexation reaction modified to an isoelectric reaction showed a satisfactory prediction of in the temperature range of 10-70 °C. Finally, the results of U(vi) speciation in groundwater indicated that the dominance of calcium uranyl tricarbonate complexes would be weakened at elevated temperatures by the strongly enhanced hydrolysis of U(vi).

Uranium(VI) sorption complexes on silica in the presence of calcium and carbonate.

Uranium sorption on minerals and related solids depends to a large degree on its aqueous speciation. The present work attempts to understand the U(VI) sorption behavior on silica under environmentally relevant conditions, i.e. at neutral to weakly alkaline pH and in the presence of dissolved calcium and carbonate. Under these conditions, Ca(UO2)(CO3)32- and Ca2(UO2)(CO3)3(aq) complexes emerge as the dominant aqueous U(VI) species. The U(VI) sorption affinity was measured as a function of contact time, solution pH, and humic acid. The U(VI) sorption decreased with increase of pH and was not affected by the addition of 50 mg/L humic acid. On the other hand, nitric acid was more effective than EDTA and carbonate at desorbing U(VI). Generally, the U(VI) sorbed on silica at neutral pH was less readily desorbed than that sorbed at higher pH values. Therefore, the U(VI) complex favorably sorbed on silica at the neutral pH is more strongly bound to the silica surface than that sorbed at higher pH values. Time-resolved laser fluorescence spectroscopy confirmed the results of the batch sorption experiments and revealed the presence of two surface U(VI) complexes with fluorescence lifetimes 251 ± 8 µs and 807 ± 24 µs.