Detection Of Uranium Research Articles

Determination of trace uranium concentrations in spent‐fuel reprocessing using online graphite crystal pre‐diffraction energy‐dispersive x‐ray fluorescence

AbstractAn online graphite crystal pre‐diffraction x‐ray fluorescence technique was developed for accurate real‐time detection of trace uranium concentrations in spent‐fuel reprocessing streams. Online analysis for determining uranium concentrations was established. The device was equipped with measurement windows in both the flow cell and a side wall of the glove box. X‐ray tubes and detectors were arranged outside the glove box, and the process stream flowing through the flow cell was measured through the measurement window. A cylindrical highly oriented pyrolytic graphite crystal was located in front of the detector to improve detection efficiency and to provide monochromatic uranium‐characteristic x‐rays. At the same time, the device could perform remote online automatic calibration. The uranium detection limit in a kerosene solution was 0.08 mg/L, and the quantitative limit was 0.27 mg/L. The detection limit in a nitric acid solution was 0.11 mg/L, and the quantitative limit was 0.37 mg/L. The relative standard deviation of measuring 0.5 mg/L uranium was less than 10%, which greatly improved online monitoring of trace uranium in spent‐fuel reprocessing samples.

Redox-active sp2-c connected metal covalent organic frameworks for selective detection and reductive separation of uranium

It is economically desirable to develop a material that can simultaneously detect and recover uranium. Herein, a CC-bridged two-dimensional metal-covalent organic framework (Cu-BTAN-AO MCOF) was constructed by condensation of metal single crystals with a rigid structure (Cu3(PyCA)3) and cyano monomers (BTAN) via Knoevenagel reaction for simultaneous detection and adsorption of uranium. The amidoxime group within the pore and the presence of unsaturated Cu(I) in the framework facilitate the adsorption of uranyl ions onto the amidoxime group, leading to fluorescence quenching via the photoinduced electron transfer (PET) mechanism, achieving a detection limit of as low as 167 nM uranyl ions. Furthermore, Cu-BTAN-AO demonstrates exceptional efficiency in capturing uranium from wastewater characterized by rapid kinetics and superior selectivity. It is noteworthy that Cu-BTAN-AO is the first example of simultaneous detection, adsorption and chemical reduction of uranium using metal centers and functional groups in MCOF, indicating that Cu-BTAN-AO has great potential for the detection and recovery of uranium-containing wastewater. This design strategy may also be applicable to advancing sensing and energy materials for other important metal ions.

Field Detection of Uranyl in Coastal Water of China Using a Portable Device via DNA Photocleavage.

The urgent need for field detection of uranium in seawater is 2-fold: to provide prompt guidance for uranium extraction and to prevent human exposure to nuclear radiation. However, current methods for this purpose are largely hindered by bulky instrumentation, high costs of developed materials, and severe matrix interferences, which limit their further application in the field. Herein, we demonstrated a portable and label-free strategy for the field detection of uranyl in seawater based on the efficient photocleavage of DNA. Further experiments confirmed the generation of ultraviolet (UV) light-induced reactive oxygen species (ROS), such as O2•- and •OH, which fragmented oligomeric DNA in the presence of uranyl and UV light. Detailed studies showed that DNA significantly enhances uranyl absorption in the UV-visible region, leading to the generation of more ROS. A fluorescence system for the selective detection of uranyl in seawater was established by immobilizing two complementary oligonucleotides with the fluorescent dye SYBR Green I. The strategy of UV-induced photocleavage offers high selectivity, excellent interference immunity, and high sensitivity for uranyl, with a detection limit of 6.8 nM. Additionally, the fluorescence can be visually detected using a 3D-printed miniaturized device integrated with a smartphone. This method has been successfully applied to the on-site detection of uranyl in seawater in 18 Chinese coastal cities and along the coast of Hainan Island within 3 min for a single sample. The sample testing and field analysis results indicate that this strategy has promising potential for real-time monitoring of trace uranyl in China's coastal waters. It is expected to be utilized for the rapid assessment of nuclear contamination and nuclear engineering construction.

Properties and mechanism of uranium adsorption on single-sided fluorinated graphene: A first-principles study

Functionalized two-dimensional materials have been widely explored as possible candidates to adsorb radioactive nuclide due to their large specific surface and tunable properties. In this work, single-sided fluorinated graphene (ssFG) with different fluorinated rates have been predicted to be an effective adsorbent for uranium atoms using density functional theory (DFT) simulations. The linear response method was used to obtain a more accurate Hubbard U value (3.1 eV) of the 5f orbital of the uranium atom. Our calculated results show that uranium atoms were energetically favorable adsorbed on the C2F, C6F, C8F ssFGs, and their adsorption energies are 3.45, 1.20, and 1.12 eV, respectively. The electronic analysis, such as the density of states, charge transfer and differential charge density suggest that the uranium atom has the strongest chemisorption with the substrate C2F. C2F also exhibits excellent performance in terms of the adsorption capacity of uranium atoms. In addition, the critical temperature for the adsorption-desorption transition of uranium atoms was predicted to be 632 K by the adsorption rate equation. The results suggest that ssFG, especially C2F, was a promising material for uranium adsorption, have promising application in nuclear waste disposal, extraction of uranium from seawater, uranium detection, etc.

Uranium Single Particle Analysis for Simultaneous Fluorine and Uranium Isotopic Determinations via Laser-Induced Breakdown Spectroscopy/Laser Ablation-Multicollector-Inductively Coupled Plasma-Mass Spectrometry.

Uranyl fluoride (UO2F2) particles (<20 μm) were subjected to first-of-its-kind analysis via simultaneous laser-induced breakdown spectroscopy (LIBS) and laser ablation multi-collector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS). Briefly, a nanosecond pulsed high-energy laser was focused onto the sample (particle) surface. In a single laser pulse, the UO2F2 particle was excited/ionized within the microplasma volume, and the emission of light was collected via fiber optics such that emission spectroscopy could be employed for the detection of uranium (U) and fluorine (F). The ablated particle was simultaneously transported into the MC-ICP-MS for high precision isotopic (i.e., 234U, 235U, and 238U) analysis. This method, LIBS/LA-MC-ICP-MS was optimized and employed to rapidly measure 80+ UO2F2 particles, which were subjected to different calcination processes, which results in varying degrees of F loss from the individual particles. In measuring the particles, the average F/U ratios for the populations treated at 100 and 500 °C were 2.78 ± 1.28 and 1.01 ± 0.50, respectively, confirming loss of F through the calcination process. The average 235U/238U on the particle populations for the 100 and 500 °C were 0.007262 (22) and 0.007231 (23), which was determined to be <0.2% from the expected value. The 234U/238U ratios on the same particles were 0.000053 (11) and 0.000050 (10) for the 100 and 500 °C, respectively, <10% from the expected value. Notably, each population was analyzed in under 5 min, demonstrating the truly rapid analysis technique presented here.

Analysis of Thorium (Th) and Uranium (U) in radioactive wastewater sample in accordance with American Public Health Association (APHA) 3125 method

The main issue with thorium (Th) and uranium (U) in radioactive wastewater is the potential of these elements to contaminate the water bodies. The unregulated radioactive wastewater release can affect the ecosystem and potentially harm aquatic life. Therefore, there is a need to establish the analysis of Th and U using standard method to obtain better sensitivity and good confidence in the final report. In this study, the determination of uranium and thorium was employed using the American Public Health Association (APHA) method 3125 standard method. The method performance and method detection level (MDL) samples for APHA 3125 were prepared in the deionized water and digested using hot block (APHA 3030E) and microwave digester (APHA 3030K). The quantification of 238U, 235U and 232Th in the method performance and MDL samples was performed using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). From the results, the method performance samples for both digestion methods were in accordance with the APHA requirement. The MDL obtained from APHA 3030E for 232Th, 238U, and 235U were 5, 7, and 8 μg L−1 respectively. Meanwhile, the MDL obtained from the microwave digester for 232Th, 238U, and 235U, and were 2, 3, and 3 μg L−1 respectively. The APHA 3030K digestion technique gives lower and better detection limit compared to the APHA 3030E technique. Based on APHA 3030K MDL, 232Th was detected in the radioactive wastewater sample while 238U and 235U were less than MDL. Meanwhile, for APHA 3030E, all elements were below MDL. This study will enhance the detection of uranium and thorium in the radioactive wastewater sample towards better environmental monitoring programs at the national and global levels.

Water-soluble, SDS-functionalized CdSe/CdS/ZnS quantum dots for uranium detection in aqueous environments

Water-soluble fluorescent probes for conveniently and rapidly monitoring the hazardous uranyl ions (UO22+) in nuclear wastewater are crucial for public nuclear security. Herein, we demonstrated a water-soluble CdSe/CdS/ZnS QDs probe by substituting hydrophilic dodecyl sodium sulfate (SDS) ligands for the original hydrophobic oleic acid ligands toward the rapid and accurate detection of trace UO22+ in aqueous environments. From this simple ligand exchange mothed, the as-prepared QDs probe exhibited a narrow full width at half maximum (FWHM) of 53 nm with an emission peak at 666 nm. Benefiting from dynamic and static fluorescence quenching interaction, this probe represented a high sensitivity (a detect limit of 15.4 nM), a high selectivity with comparison of presettable eight metal ions), a high environmental stability (a recovery rate of 81–94 %) and a rapid inspection ability (on the order of a few minutes). Therefore, this work provided a new approach for the determination of UO22+ in aqueous environments and then for the assurance of public nuclear security.

Advanced “turn-on” colorimetric uranium platform based on the enhanced nanozyme activity of a donor-acceptor structured covalent organic framework

BackgroundThe increasing uranium containing wastes generated during uranium mining and finishing pose a huge threat to the environment and human health, and thus robust strategies for on-site monitoring of uranium pollutant are of great significance for environmental protection around uranium tailings. ResultsHerein, a facile “turn-on” colorimetric platform that can achieve uranium detection by spectrometry and naked eyes was developed based on the uranium-enhanced nanozyme activity of covalent organic framework (JUC-505). Thanks to the extended π-conjugated skeleton and donor-acceptor (D-A) structure, JUC-505 exhibited superior photo-activated nanozyme activity, which would be prohibited when the cyano group in JUC-505 skeleton was transformed to the amidoxime group. Further results elucidated that the coordination of uranium with amidoxime groups led to the electron transfer between uranium and the JUC-505-AO skeleton, and thus significantly restored the nanozymatic activity of JUC-505-AO with the subsequent remarkable color changes. Moreover, the uranium concentrations in uranium tailing wastewater detected by the present “turn-on” colorimetric method were well agreed with those by ICP-MS, demonstrating a high accuracy of the present method in real samples. SignificanceThe D-A structured JUC-505 with superior photocatalytic property and nanozymatic activity was applied to facilitate colorimetric detection of uranium, which displays the advantages of low detection limit, excellent selectivity, fast response and simple operation for uranium detection in real samples, and shows a great potential in on-site monitoring of uranium pollutant around uranium tailings as well as nuclear power plant.

Europium(III) Functionalized Covalent Organic Framework as Sensitive and Selective Fluorescent Switch for Detection of Uranium.

Uranium poses severe health risks due to its radioactivity and chemical toxicity if released into the environment. Therefore, there is an urgent demand to develop sensing materials in situ monitoring of uranium with high sensitivity and stability. In this work, a fluorescent Eu3+-TFPB-Bpy is synthesized by grafting Eu3+ cation onto TFPB-Bpy covalent organic framework (COF) synthesized through Schiff base condensation of monomers 1,3,5-tris(4-formylphenyl)benzene (TFPB) and 5,5'-diamino-2,2'-bipyridine (Bpy). The fluorescence of Eu3+-TFPB-Bpy is enhanced compared with that of TFPB-Bpy, which is originated from the intramolecular rotations of building blocks limited by the bipyridine units of TFPB-Bpy coordinated with Eu3+. More significantly, Eu3+-TFPB-Bpy is a highly efficient probe for sensing UO22+ in aqueous solution with the luminescence intensity efficiently amplified by complexation of UO22+ with Eu3+. The turn-on sensing capability was derived from the resonance energy transfer occurring from UO22+ to the Eu3+-TFPB-Bpy. The developed probe displayed desirable linear range from 5 nM to 5 μM with good selectivity and rapid response time (2 s) for UO22+ in mining wastewater. This strategy provides a vivid illustration for designing luminescence lanthanide COF hybrid materials with applications in environmental monitoring.

Covalently construction of C-GSH-AuNCs@UiO-66-NH2 composites as an efficient turn-on fluorescence sensor for UO22+

Due to the continuous expansion of the nuclear power industry, the exploitation of uranium resources has led to the discharge of large quantities of uranium-rich wastewater into the environment, which poses a major threat to the environment and human health. Rapid detection of uranium in water bodies is of great significance for early warning of uranium contamination in the environment, safe discharge and real-time regulation of nuclear waste, and sustainable development of energy and ecological environment. Herein, we report a new “turn-on” fluorescent sensor for the detection of UO22+ in aqueous solutions. The fluorescent sensor was obtained by covalently bonding UiO-66-NH2 with gold nanoclusters GSH-AuNCs and showed a sensitive fluorescence enhancement response to UO22+ at low solid-liquid ratio, with a detection limit of 15.3 nmol L−1. With the advantages of intuitive visual detection, reusability and easy separation, the sensitive fluorescence sensor has great potential for the detection of UO22+ in aqueous solutions.

Fabricating Covalent–Organic Quantum Dots through Selective Disassembly of Hydrogen-Covalent Hybridized Organic Frameworks for Efficient and Sensitive Uranium Detection

Fabricating Covalent–Organic Quantum Dots through Selective Disassembly of Hydrogen-Covalent Hybridized Organic Frameworks for Efficient and Sensitive Uranium Detection

An approach for collaboratively separation and detection of uranium based on novel plastic scintillating resin

It is extremely significant to monitor the radioactive uranium during the process of nuclear energy mining and disposal because of its high levels of chemical and radiological toxicity. In this work, a novel uranium plastic scintillator resin (U-PSresin) was successfully synthesized by suspension polymerization and used to rapidly enrich and determine uranium by Liquid Scintillation Counting (LSC). The U-PSresin shows excellent irradiation stability, extremely appropriate adsorption capacity of U(VI) (9.35 mg/g), which is convenient for the accurate measurement of LSC. Meanwhile, U-PSresin has a deviation of less than 5 % in adsorption and measurement repeatability and can be utilized to accurately measure more than 1 mg of natural uranium after enrichment. For different types of spiked water samples, the measurement deviation of U-PSresin is less than 15 %. This work demonstrates that U-PSresin can selectively enrich and quantitatively measure uranium in an aqueous environment, showcasing its significant potential in nuclear emergency scenarios and environmental monitoring.

Dual-functional metal-organic frameworks-based hydrogel micromotor for uranium detection and removal

Self-propelled micro/nanomotors have attracted great attention for environmental remediation, however, their use for radioactive waste detection and removal has not been addressed. Engineered micromotors that are able to combine fast detection and highly adsorptive capability are promising tools for radioactive waste management but remain challenging. Herein, we design self-propelled micromotors based on zeolite imidazolate framework (ZIF-8)-hydrogel composites via inverse emulsion polymerization and show their potential for efficient uranium detection and removal. The incorporation of magnetic ferroferric oxide nanoparticles enables the magnetic recycling and actuation of the single micromotors as well as formation of swarms of worm-like or tank-treading structure. Benefited from the enhanced motion, the micromotors show fast and high-capacity uranium adsorption (747.3 mg g−1), as well as fast uranium detection based on fluorescence quenching. DFT calculation confirms the strong binding between carboxyl groups and uranyl ions. The combination of poly(acrylic acid-co-acrylamide) with ZIF-8 greatly enhances the fluorescence of the micromotor, facilitating the high-resolution fluorescence detection. A low detection limit of 250 ppb is reached by the micromotors. Such self-propelled micromotors provide a new strategy for the design of smart materials in remediation of radioactive wastewater.

Fluorescent Eu-MOF@nanocellulose-based nanopaper for rapid and sensitive detection of uranium (Ⅵ)

Radioactive uranium leaks into natural water bodies mainly in the form of uranyl ions (UO22+), posing ecological and human health risks. Fluorescent europium-based metal-organic frameworks (Eu-MOFs) have been demonstrated to be effective fluorescent sensors for UO22+, but the large size, powder state and poor dispersity limit their further application. In this work, fluorescent Eu-MOFs were in-situ grown on TEMPO-oxidized cellulose nanofibers (TOCNFs), which is the first time that spherical Eu-MOF crystals with sizes below 10 nm were prepared. Fluorescence spectral analysis revealed a nine-fold increase in the fluorescence intensity of TOCNF@Eu-MOF compared to Eu-MOF. The nanocomposites achieved rapid and sensitive fluorescence quenching to UO22+ through the “antenna effect” and unsaturated Lewis basic sites on the ligands binding with UO22+. Moreover, TOCNF@Eu-MOF demonstrated excellent selectivity and anti-interference for UO22+ detection. For the nanopaper-based sensor made from TOCNF@Eu-MOF, the Stern-Volmer quenching constant (KSV) was calculated as 8.21 × 104 M−1, and the lowest limit of detection (LOD) was 6.6 × 10−7 M, significantly lower than the 1.32 × 10−6 M of Eu-MOFs. In addition, the nanopaper exhibited good fluorescence stability and cyclic detection performance, enabling the rapid and convenient detection of UO22+ in the aqueous phase within 30 s by simple dipping.

Measurement of uranium in a glass matrix based on spatial confinement using fiber-optic laser-induced breakdown spectroscopy

The storage and management of nuclear waste materials require the detection of uranium, but traditional analytical methods are unsuitable for radioactive environments.

Quantitative performance improvement using beam shaping plasma modulation for uranium detection in di-uranate using laser-induced breakdown spectroscopy

LIBS with beam shaping plasma modulation technology can reduce spectral interference and improve the quantitative performance of uranium in di-uranate.

One particle three targets: Phosphate anion-modified magnetic mesoporous silica with enhanced fluorescence for sensitive detection, efficient adsorption, and repeated removal of uranium (VI) ions

An ideal adsorbent material that combines the multiple capabilities of sensitive detection, efficient adsorption, and repeatable removal of uranium (U) from the environment remains a serious challenge. Herin, a general method was developed for synthesizing a series of phosphate anions (such as: PO43-, P2O74-, P3O105- and P6O186-) modified magnetic mesoporous silica nanoparticles (Fe3O4 @mSiO2-Zn2+ NPs). The mesoporous surfaces and abundant phosphate groups provide potential, powerful uranium-binding sites for capturing U(VI) ions. Especially, the optimum adsorption capacity of Fe3O4 @mSiO2-Zn2+/P3O105- NPs was as high as 885.90 mg·g−1 (298 K), which was higher than that of unmodified or other phosphate anions-modified Fe3O4 @mSiO2-Zn2+ NPs. Meanwhile, P3O105--binding sites and mesoporous surfaces also strongly restrict U(VI) ions’ fluorescence vibrational inactivation, the adsorption results in rapid green fluorescence enhancement (within 180 s), and an ultra-low detection limit (4.5 nmol·L–1), which is well below the standard in drinking water of the World Health Organization (WHO). Furthermore, even after 5 cycles, the adsorbent still maintained their original adsorption capacity of 80.21% and displayed excellent selectivity for detecting and removing U(VI) from seawater. Based on these results, the Fe3O4 @mSiO2-Zn2+/P3O105- NPs seem to be a suitable multifunctional adsorbent for the detection, adsorption, and removal of U(VI) from environment.

Recent advancement in nanomaterials for the detection and removal of uranium: A review

Uranyl ions U(VI), are the common by-product of nuclear power plants and anthropogenic activities like mining, excess utilization of fertilizers, oil industries, etc. Its intake into the body causes serious health concerns such as liver toxicity, brain damage, DNA damage and reproductive issues. Therefore, there is urgent need to develop the detection and remediation strategies. Nanomaterials (NMs), due to their unique physiochemical properties including very high specific area, tiny sizes, quantum effects, high chemical reactivity and selectivity have become emerging materials for the detection and remediation of these radioactive wastes. Therefore, the current study aims to provide a holistic view and investigation of these new emerging NMs that are effective for the detection and removal of Uranium including metal nanoparticles, carbon-based NMs, nanosized metal oxides, metal sulfides, metal-organic frameworks, cellulose NMs, metal carbides/nitrides, and carbon dots (CDs). Along with this, the production status, and its contamination data in food, water, and soil samples all across the world are also complied in this work.

Design and Fabrication of Hypercrosslinked Covalent Organic Adsorbents for Selective Uranium Extraction.

Uranium detection and extraction are necessary for the ecological environment as the growing demand for nuclear energy. Hence, exploring stable materials with excellent performance in uranium extraction and detection is highly desired. Herein, by amidoxime-functionalizing tetrafluoroterephthalonitrile (TFTPN) crosslinked hydroquinone (bP), phloroglucinol (tP), and 4,4',4″-trihydroxytriphenylmethane (tBP), three covalent organic polymers (COPs) bPF-AO, tPF-AO, and tBPF-AO with different crosslinked architectures are fabricated. Uranium extraction and detection related to the difference in molecule construction were systemically investigated, giving some reference for the rational design and fabrication of advanced materials for the removal and monitoring of uranium in the environment. The tPF-AO with a compact steric structure achieves the highest theoretical maximum adsorption capacity of 578.9 ± 15.2 mg g-1 and the best recyclability. The scattering electron center and U(VI) selective binding sites endow tBPF-AO with excellent capability in selective detection for U(VI), with a limit of detection of 24.2 nmol L-1, which is well below the standard for U(VI) in drinking water of the World Health Organization (WHO). Moreover, the COPs possess prominent physicochemical stability and recyclability, and more importantly, the PAE-based COPs are derived from inexpensive industry materials with easy processing methods, providing an efficient and economical way for the detection and adsorption of uranium.

Constructing an ultrastable imidazole covalent organic framework for concurrent uranium detection and recovery

Uranium is one of the most important strategic resources for the development of the nuclear industry, but its unintended release has created potential environmental and health risks. It is highly desired to explore new methods that enable concurrent uranium monitoring and recovery for environmental protection and sustainable development of the nuclear industry. Here, for the first time, an imidazole fluorescent covalent organic framework (named PyTT-Tp) with ultrastable skeleton and open nanopore channel is synthesized by condensing ammonium acetate, 1,3,5-triformylphloroglucinol and pyrene-4,5,9,10-tetrone. By precisely tailoring complexing ligands, PyTT-Tp shows an excellent uranium recovery capacity of 941.27 mg g−1 and reached equilibrium within 60 min, which can be attributed to dense selective uranium binding sites on the highly accessible open skeleton. In addition, due to the signal amplification of the pyrene-imidazole skeleton, it has an ultra-low detection limit of 4.92 nM UO22+ and an ultra-fast response time (2 s) suitable for on-site monitoring the uranium content of the extracted water. By modulating target complexing ligands, this approach can be extended to the monitoring and recovery of other strategic nuclides.