Total Reflection X-ray Fluorescence Spectrometric Analysis of Ten Lanthanides at the Ultratrace Level Having a High Degree of Overlap in the Emission Lines.

The extensive use of lanthanide elements in the medical, electrical, agricultural, and nuclear fields has increased their contamination in the environment. The detrimental effect of lanthanides on human health can be reduced or eliminated by their fast determination in the concerned specimen. For this purpose, an offline conjugation of the cloud point extraction (CPE) process with total reflection X-ray fluorescence (TXRF) spectrometry was done. This process was found to provide simple, quick, and precise simultaneous determination of ten lanthanides whose emission lines have a high degree of overlap at the ultratrace level. N,N,N',N'-tetra-octyl-diglycolamide in triton X-114 micelles was found to offer a selective CPE of all of the lanthanides in the presence of higher concentrations of naturally abundant cations and anions. A multivariative partial least-squares regression (PLSR) calibration approach was preferred due to the complex overlapped spectra of L lines of the lanthanides. Ten lanthanides, viz., La, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm, and Lu, were simultaneously determined by this method, having concentrations in the range from 10 to 5 × 103 µg L-1. The proposed method was validated by analyzing three certified reference materials (CRMs), viz., NASS-7 seawater, SRLS-6 river water, and NIST 1640a natural water, via standard addition with the relative standard deviations of ≤10%.

Synthesis and feasibility studies of doping U at Ti site of Y2Ti2O7 as a radioactive waste immobilization matrix.

In pursuit of clean and green nuclear energy one of the major challenges is to effectively immobilize the nuclear waste. In this context A2B2O7 type pyrochlore owing to its structural flexibility, ability to accommodate ions at both A/B-sites and high radiation tolerance has demonstrated excellent capability to store highly radioactive actinide ions. To fill the major gap area of actinide doping at the B site we have taken up the challenge of doping uranium ions at the Ti site of Y2Ti2O7 type pyrochlore. An yttria titanate (Y2Ti2-xUxO7; x = 0.05, 0.075, 0.1, 0.2, and 0.3) based matrix with uranium doped at the Ti site was synthesized using a simple gel combustion route under an air atmosphere. Rietveld refined X-ray diffraction (XRD) demonstrated that Y2Ti2O7 can accommodate U up to 5 mol% in the Ti site without any phase separation, which was further confirmed using Raman spectroscopy. Y2Ti2O7 based matrices are found to be radiation stable up to 1000 kGy and at the same time they are moderately thermally stable and on a par with the values reported for pyrochlores. Uranium in Y2Ti2O7 stabilizes in +6 oxidation state in the form of uranyl ion distributed near and far off from titanium vacancies with distinct excited state lifetime. This work could provide a smart and strategic way for selecting a suitable advanced ceramic matrix for immobilization of high level waste with additional and important information on solubility limit, actinide speciation, radiation/thermal stability, actinide concentration, etc.

γ-Resistant Microporous CAU-1 MOF for Selective Remediation of Thorium.

A simple solvothermal method was used to synthesize a metal-organic framework (MOF) with an Al metal entity, viz., CAU-1 NH2. The synthesized MOF was characterized using different techniques like X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy (SEM), field emission SEM (FE-SEM), transmission electron microscopy, small-angle X-ray scattering, positron annihilation lifetime spectroscopy, and X-ray photoelectron spectroscopy. The radiation stability was evaluated by irradiating the material up to a cumulative dose of 2 MGy using 60Co for the first time. The studies showed a remarkable gamma irradiation stability of the material up to 1 MGy. The porosity and surface area of the synthesized MOF were determined by Brunauer-Emmett-Teller, which showed a high specific surface area of 550 m2/g. The pH dependence study of Th uptake from an aqueous solution was performed from pH 2-8, followed by adsorption isotherm and adsorption kinetics studies. These results revealed that the Langmuir and pseudo-second-order kinetic models can be well adapted for understanding the Th uptake and kinetics, respectively. The synthesized MOF exhibited an ∼404 mg/g thorium adsorption capacity. Selectivity studies of adsorption of Th w.r.t. to U and different metal ions such as Cu, Co, Ni, and Fe showed that Th gets adsorbed preferentially as compared to other metal ions. In addition, the MOF could be used multiple times without much deterioration.

A highly sensitive method for uranium quantification in water samples at ultra-trace level by total reflection X-ray fluorescence, after its direct pre-concentration on the surface of amidoxime functionalized quartz sample supports.

In this work we have developed a Total reflection X-Ray Fluorescence (TXRF) based methodology for the determination of uranium in natural water samples at ultra-trace concentration level. The methodology involves functionalization of quartz sample supports used for TXRF measurements with (3-Amidoxy) triethoxysilane, which has very high uranium uptake efficiency. (3-Amidoxy) triethoxysilane has been synthesized from (3-Cyanopropyl) triethoxysilane (CPTS). This amidoxime functionalized sample supports, simply needed to be dipped in the uranium solution for 3 h after which, it can be directly taken for TXRF measurements. The developed methodology is very fast, simple with less sample preparation steps involved. The present work utilizes Rayleigh scattered peak to construct the calibration curve for the quantification purpose. The developed methodology has improved accuracy as well as precision for the quantification of uranium at such low concentrations level. The detection limit and accuracy obtained are 0.013 ng/mL (13 ppt) and 1.9%, respectively which are the lowest using any X-Ray Fluorescence based method, to the best of our knowledge. The method was successfully applied for the U determination in natural water samples like ground water, river water and sea water.

Mechanism of CO + N2O reaction via transient CO3(2-) species over crystalline Fe-substituted lanthanum titanates.

Some newer mechanistic aspects investigated by in situ Fourier transform infrared (FTIR) in conjunction with catalytic activity under similar conditions over crystalline lanthanum titanates as a function of Fe substitution at the B-site for the CO + N(2)O reaction are reported for the first time in the present communication. La(2)Ti(2(1-x))Fe(2x)O(7-delta) (0.0 < or = x < or = 1.0) was synthesized by gel combustion where Fe(3+) substitution effectively enhanced the conversion rates for N(2)O reduction as compared to the pristine La(2)Ti(2)O(7) (LTOGC). Among all samples, maximum conversion over La(2)Ti(0.8)Fe(1.2)O(7-delta) [LF(0.6)GC] catalyst was observed. In situ FTIR results reveal that substitution-induced anionic vacancies/defects provide additional sites on the surface of LF(0.6)GC for CO chemisorptions, whereas a perfect stoichiometric lattice like LTOGC is devoid of such sites. Surface-adsorbed CO reacts with surface lattice oxygen in the case of nonstoichiometric LF(0.6)GC to produce carbonates (M-CO(3)(2-)) at a much lower temperature. The reaction proceeds via carbonate formation, leaving the catalytic surface oxygen deficient in LF(0.6)GC, and therefore facilitates the reduction of preadsorbed, N(2)O [N(2)O(g) + * --> N(2) + *-O) by easily adsorbing the oxygen species (*-O) generated in N(2)O reduction, which is subsequently driven away by adsorbed/gas phase CO, whereas in the case of LTOGC, progress of the reaction was sluggish in the absence of transient carbonate species. Dissociative chemisorptions of N(2)O are not facilitated on stoichiometric oxygen excess titanate, as there is no vacancy in the surface to accommodate another oxygen atom. The redox mechanism via CO(3)(2-) species is proposed for CO + N(2)O reaction over La(2)Ti(2(1-x))Fe(2x)O(7-delta), as against the associative mechanism observed in the unsubstituted sample, La(2)Ti(2)O(7), as suggested by in situ FTIR in conjunction with catalytic activity results.