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ACS Omega May 2022The actinide lanthanide separation (ALSEP) process is a modern solvent extraction approach used for the separation of the minor actinides americium and curium from the...
The actinide lanthanide separation (ALSEP) process is a modern solvent extraction approach used for the separation of the minor actinides americium and curium from the lanthanide fission products for transmutation, a process that can significantly reduce the long-term radioactivity and heat loading of nuclear waste. This process, inspired by existing chemistry, uses the aminopolycarboxylate -(2-hydroxyethyl)ethylenediamine-,,-triacetic acid (HEDTA) to selectively separate the actinides by stripping them from the organic phase while leaving the lanthanides behind. HEDTA is used in this separation as it has been shown to exhibit faster extraction kinetics than other aminopolycarboxylates, but its lower coordination number can allow for the formation of higher order complexes with the typically 8- to 9-coordinate f-elements. ALSEP uses a carboxylic acid buffer in the aqueous phase to control the pH of the system during metal stripping, and this buffer has the ability to complex actinide(III) and lanthanide(III) ions. The presence of a previously uncharacterized ternary lanthanide-HEDTA-citrate complex was detected during single-phase spectroscopy experiments. A combination of partitioning experiments and spectrophotometric titrations led to the identification of a 1:1:1 complex containing a partially protonated citrate ligand and determination of the stability constant of its neodymium complex.
PubMed: 35557699
DOI: 10.1021/acsomega.2c00759 -
RSC Advances Nov 2021Solvent extraction of Eu and Am ,,','-tetraoctyl diglycolamide (TODGA) dissolved in different molecular diluents was studied. The diluent types used in this work were...
Solvent extraction of Eu and Am ,,','-tetraoctyl diglycolamide (TODGA) dissolved in different molecular diluents was studied. The diluent types used in this work were primary and secondary alcohols, secondary ketones and alkanes. Effects of concentration of extracting agent, temperature, diluent type and its carbon chain length on the extractions were determined. Distribution ratios of Eu and Am showed high dependence on the diluent type as well as the carbon chain length within the same type of diluent. The highest distribution ratios for both Eu and Am as well as the separation factors of Eu over Am were observed in the alkane diluents. Unexpectedly high distribution ratios for Eu and Am were observed in polar diluents with 5 carbon atoms in the chain, clearly standing out against the general trends. It was found that Eu and Am extraction TODGA is enthalpy driven in all the studied diluents and that extraction is more exothermic in alkane diluents. Analysis of the stoichiometry of the extracted complexes shows that the average ligand number of TODGA molecules in the extracted complex is lower for Am compared to Eu except for with alkane diluents.
PubMed: 35494375
DOI: 10.1039/d1ra07534a -
Health Physics Jun 2021In the nuclear industry, wound contamination with americium is expected to increase with decommissioning and waste management. Treatment of workers with...
In the nuclear industry, wound contamination with americium is expected to increase with decommissioning and waste management. Treatment of workers with diethylenetriaminepentaacetic acid (DTPA) requires optimization to reduce internal contamination and radiation exposure. This work aimed at evaluating and comparing different DTPA protocol efficacies after wound contamination of rats with americium. Wound contamination was simulated in rats by depositing americium nitrate in an incision in the hind limb. Different routes, times, and frequencies of DTPA administration were evaluated. Individual daily urinary americium excretion and tissue retention were analyzed using the statistical tool STATBIODIS. Urinary profiles, urinary enhancement factors, and inhibition percentages of tissue retention were calculated. A single DTPA administration the day of contamination induced a rapid increase in americium urinary excretion that decreased exponentially over 7 d, indicating that the first DTPA administration should be delivered as early as possible. DTPA treatment limited americium uptake in systemic tissues irrespective of the protocol. Liver and skeleton burdens were markedly reduced, which would drive reduction of radiation dose. Local or intravenous injections were equally effective. Inherent difficulties in wound site activity measurements did not allow identification of a significant decorporating effect at the wound site. Repeated intravenous injections of DTPA also increased americium urinary excretion, which supports the use of multiple DTPA administrations shortly after wound contamination. Results from these statistical analyses will contribute to a better understanding of americium behavior in the presence or absence of DTPA and may aid optimization of treatment for workers.
Topics: Americium; Animals; Chelating Agents; Liver; Pentetic Acid; Plutonium; Radiation Exposure; Rats
PubMed: 33577223
DOI: 10.1097/HP.0000000000001384 -
CrystEngComm Sep 2022This paper details the first dedicated production of homogeneous nanocrystalline particles of mixed actinide oxide solid solutions containing americium. The target...
This paper details the first dedicated production of homogeneous nanocrystalline particles of mixed actinide oxide solid solutions containing americium. The target compositions were UPuAmO, UAmO and UAmO. After successful hydrothermal synthesis and chemical characterisation, the nanocrystals were sintered and their structure and behaviour under self-irradiation were studied by powder XRD. Cationic charge distribution of the as-prepared nanocrystalline and sintered UAmO materials was investigated applying U M and Am M edge high energy resolution XANES (HR-XANES). Typical oxidation states detected for the cations are U(iv)/U(v) and Am(iii)/Am(iv). The measured crystallographic swelling was systematically smaller for the as-synthesised nanoparticles than the sintered products. For sintered pellets, the maximal volumetric swelling was about 0.8% at saturation, in line with literature data for PuO, AmO, (U,Pu)O or (U,Am)O.
PubMed: 36275942
DOI: 10.1039/d2ce00527a -
Materials (Basel, Switzerland) Apr 2022Polymers have an excellent effect in terms of moderating fast neutrons with rich hydrogen and carbon, which plays an indispensable role in shielding devices. As the...
Polymers have an excellent effect in terms of moderating fast neutrons with rich hydrogen and carbon, which plays an indispensable role in shielding devices. As the shielding of neutrons is typically accompanied by the generation of γ-rays, shielding materials are developed from monomers to multi-component composites, multi-layer structures, and even complex structures. In this paper, based on the typical multilayer structure, the integrated design of the shield component structure and the preparation and performance evaluation of the materials is carried out based on the design sample of the heat-resistant lightweight polymer-based interlayer. Through calculation, the component structure of the polymer-based materials and the three-layer thickness of the shield are obtained. The mass fraction of boron carbide accounts for 11% of the polymer-based material. Since the polymer-based material is the weak link of heat resistance of the multilayer shield, in terms of material selection and modification, the BC/TiO/polyimide molded plate was prepared by the hot-pressing method, and characterization analysis was conducted for its structure and properties. The results show that the ball milling method can mix the materials well and realize the uniform dispersion of BC and TiO in the polyimide matrices. Boron carbide particles are evenly distributed in the material. Except for Ti, the other elemental content of the selected areas for mapping is in good agreement with the theoretical values of the elemental content of the system. The prepared BC/TiO/polyimide molded plate presents excellent thermal properties, and its glass transition temperature and initial thermal decomposition temperature are as high as 363.6 °C and 572.8 °C, respectively. In addition, the molded plate has good toughness performs well in compression resistance, shock resistance, and thermal aging resistance, which allows it to be used for a long time under 300 °C. Finally, the prepared materials are tested experimentally on an americium beryllium neutron source. The experimental results match the simulation results well.
PubMed: 35591313
DOI: 10.3390/ma15092978 -
Health Physics Sep 2010Commonly used water-soluble polyaminocarboxylic acid (PACA) chelators, such as EDTA and DTPA, require intravenous or subcutaneous administration due to their poor...
Commonly used water-soluble polyaminocarboxylic acid (PACA) chelators, such as EDTA and DTPA, require intravenous or subcutaneous administration due to their poor bioavailability. The bioavailability of PACAs can be improved by the addition of differing lengths of alkyl side chains that alter amphipathic properties. Orally administered amphipathic triethylenetetramine pentaacetic acid (TT) compounds are efficacious for decorporation of plutonium and americium. The synthesis, efficacy, binding affinities, and some initial pharmacokinetics properties of amphipathic TT chelators are reviewed. C-labeled C12TT and C22TT chelators are reasonably well absorbed from the intestine and have a substantial biliary/fecal excretion pathway, unlike DTPA, which is mostly excreted in the urine. Whole body retention times are increased as a function of increasing lipophilicity. Neutron-induced autoradiography studies demonstrate that the oral administration of the chelators can substantially inhibit the redistribution of Pu in skeletal tissues. In summary, amphipathic TT-based chelators have favorable bioavailability, have a significant biliary excretion pathway, have demonstrated efficacy for americium and plutonium, and are thus good candidates for further development. Furthermore, some of the pharmacological properties can be manipulated by changing the lengths of the alkyl side chains and this may have some advantage for decorporation of certain metals and radionuclides.
Topics: Acetates; Administration, Oral; Americium; Autoradiography; Biological Availability; Carbon Radioisotopes; Chelating Agents; Decontamination; Intestinal Absorption; Pentetic Acid; Plutonium; Trientine
PubMed: 20699705
DOI: 10.1097/HP.0b013e3181bfb99b -
Molecules (Basel, Switzerland) Feb 2022Density functional theory (DFT) is a widely used computational method for predicting the physical and chemical properties of metals and organometals. As the number of...
Density functional theory (DFT) is a widely used computational method for predicting the physical and chemical properties of metals and organometals. As the number of electrons and orbitals in an atom increases, DFT calculations for actinide complexes become more demanding due to increased complexity. Moreover, reasonable levels of theory for calculating the structures of actinide complexes are not extensively studied. In this study, 38 calculations, based on various combinations, were performed on molecules containing two representative actinides to determine the optimal combination for predicting the geometries of actinide complexes. Among the 38 calculations, four optimal combinations were identified and compared with experimental data. The optimal combinations were applied to a more complicated and practical actinide compound, the uranyl complex (UO(2,2'-(1E,1'E)-(2,2-dimethylpropane-1,3-dyl)bis(azanylylidene)(CHOH)), for further confirmation. The corresponding optimal calculation combination provides a reasonable level of theory for accurately optimizing the structure of actinide complexes using DFT.
PubMed: 35268601
DOI: 10.3390/molecules27051500 -
ACS Omega Jan 2021A DGA-arm-grafted macrocyclic aza-crown ether ligand (Cr6DGA) was synthesized, and its solvent extraction behavior toward trivalent americium and europium in nitric acid...
Complexation and Separation of Trivalent Actinides and Lanthanides by a Novel DGA Derived from Macrocyclic Crown Ether: Synthesis, Extraction, and Spectroscopic and Density Functional Theory Studies.
A DGA-arm-grafted macrocyclic aza-crown ether ligand (Cr6DGA) was synthesized, and its solvent extraction behavior toward trivalent americium and europium in nitric acid medium was studied. The effects of various parameters such as the contact time, temperature, concentration of the extractant, and acidity on the extraction by Cr6DGA were investigated. It was found that in 3 mol/L HNO, the SF value was about 2. The complexation energies calculated by DFT showed that the Eu(III) complexes were more stable than the corresponding Am(III) complexes in gas, aqueous, and organic phases. Furthermore, the coordination study showed that the metal/ligand ratio of the extracted species was 1:2 by mass spectrometry (MS) analysis. The time-resolved laser-induced fluorescence spectra (TRLFS) further proved that the extracted species contained one water molecule, and so the composition of the extracted complexes may be [EuLNO(HO)] or [EuL(NO)(HO)]. Finally, DFT calculations revealed that [EuL(NO)(HO)] is a more stable species and the binding energy of Eu(III) with the DGA unit is lower than that with the crown unit.
PubMed: 33521455
DOI: 10.1021/acsomega.0c05317 -
Journal of Hazardous Materials Mar 2019This work evaluated sorbent materials created from nanoporous silica self-assembled with monolayer (SAMMS) of hydroxypyridinone derivatives (1,2-HOPO, 3,2-HOPO,...
This work evaluated sorbent materials created from nanoporous silica self-assembled with monolayer (SAMMS) of hydroxypyridinone derivatives (1,2-HOPO, 3,2-HOPO, 3,4-HOPO), acetamide phosphonate (Ac-Phos), glycine derivatives (IDAA, DE4A, ED3A), and thiol (SH) for capturing of actinides and transition metal cobalt. In filtered seawater doped with competing metals (Cr, Mn, Fe, Co, Cu, Zn, Se, Mo) at levels encountered in environmental or physiological samples, 3,4-HOPO-SAMMS was best at capturing uranium (U(VI)) from pH 2-8, Ac-Phos and 1,2-HOPO-SAMMS sorbents were best at pH < 2. 3,4-HOPO-SAMMS effectively captured thorium (Th(IV)) and plutonium (Pu(IV)) from pH 2-8, and americium (Am(III)) from pH 5-8. Capturing cobalt (Co(II)) from filtered river water doped with competing metals (Cu, As, Ag, Cd, Hg, Tl, and Pb) was most effective from pH 5-8 with binding affinity ranged from IDAA > DE4A > ED3A > Ac-Phos > SH on SAMMS. Iminodiacetic acid (IDAA)-SAMMS was also outstanding at capturing Co(II) in ground and seawater. Within 5 min, over 99% of U(VI) and Co(II) in seawater was captured by 3,4-HOPO-SAMMS and IDAA-SAMMS, respectively. These nanoporous materials outperformed the commercially available cation sorbents in binding affinity and adsorption rate. They have great potential for water treatment and recovery of actinides and cobalt from complex matrices.
PubMed: 30580142
DOI: 10.1016/j.jhazmat.2018.12.043