Pr(H3BNMe2BH3)3 and Pr(thd)3 as Volatile Carriers for Actinium-225. Deposition of Actinium-Doped Praseodymium Boride Thin Films for Potential Use in Brachytherapy.

Here we show that the praseodymium N,N-dimethylaminodiboranate complex Pr(H3BNMe2BH3)3 and the 2,2,6,6-tetramethylheptane-3,5-dionate complex Pr(thd)3 can serve as volatile carriers for 225Ac. The actinium coordination complexes Ac(H3BNMe2BH3)3 and Ac(thd)3 are the likely species subliming with the carrier material. A sample of 225Ac-doped Pr(H3BNMe2BH3)3 was used to deposit amorphous 225Ac-doped praseodymium boride films on glass and Si(100) at 300 °C. The α emission spectra of the refractory films are well-resolved, suggesting that they could be used as radioactive implants for brachytherapy and related treatments.

Selective separation of radium and actinium from bulk thorium target material on strong acid cation exchange resin from sulfate media.

This work presents a complete scheme for the selective separation of actinium and radium isotopes from bulk 232Th target material, in a process that may be applied in a separation scheme for the production of 225Ac by proton spallation on thorium. Thorium metal is dissolved in sulfuric acid with small amounts of HF. Actinium and radium are retained on cation exchange resin from the sulfate medium, while neutral and anionic thorium sulfate complexes are rejected. Following rinsing steps to remove residual thorium, actinium and radium are recovered from the cation exchange resin using 5 M HNO3. Further separations of actinium via extraction chromatography with UTEVA and DGA resins yield actinium in >92% yield, while providing additional decontamination from thorium and other spallation byproducts. The radium fraction can be further processed following ingrowth of 225Ac from 225Ra to produce additional 225Ac free from any potential 227Ac impurity.

An europium(III) diglycolamide complex: insights into the coordination chemistry of lanthanides in solvent extraction.

The synthesis, stoichiometry, and structural characterization of a homoleptic, cationic europium(III) complex with three neutral tetraalkyldiglycolamide ligands are reported. The tri(bismuth tetrachloride)tris(N,N,N',N'-tetra-n-octyldiglycolamide)Eu salt, [Eu(TODGA)3][(BiCl4)3] obtained from methanol was examined by Eu L3-edge X-ray absorption spectroscopy (XAS) to reveal an inner-sphere coordination of Eu(3+) that arises from 9 O atoms and two next-nearest coordination spheres that arise from 6 carbon atoms each. A structural model is proposed in which each TODGA ligand with its O=Ca-Cb-O-Cb-Ca=O backbone acts as a tridentate O donor, where the two carbonyl O atoms and the one ether O atom bond to Eu(3+). Given the structural rigidity of the tridentate coordination motif in [Eu(TODGA)3](3+) with six 5-membered chelate rings, the six Eu-Ca and six Eu-Cb interactions are readily resolved in the EXAFS (extended X-ray absorption fine structure) spectrum. The three charge balancing [BiCl4](-) anions are beyond the cationic [Eu(TODGA)3](3+) cluster in an outer sphere environment that is too distant to be detected by XAS. Despite their sizeable length and propensity for entanglement, the four n-octyl groups of each TODGA (for a total of twelve) do not perturb the Eu(3+) coordination environment over that seen from previously reported single-crystal structures of tripositive lanthanide (Ln(3+)) complexes with tetraalkyldiglycolamide ligands (of the same 1:3 metal-to-ligand ratio stoichiometry) but having shorter i-propyl and i-butyl groups. The present results set the foundation for understanding advanced solvent extraction processes for the separation of the minor, tripositive actinides (Am, Cm) from the Ln(3+) ions in terms of the local structure of Eu(3+) in a solid state coordination complex with TODGA.

Rapid methods for the isolation of actinides Sr, Tc and Po from raw urine.

Rapid methods for the isolation and analysis of individual actinides (Th, U, Pu, Am/Cm) and Sr, Tc and Po from small volumes of raw urine have been developed. The methods involve acidification of the sample and the addition of aluminum nitrate or aluminum chloride salting-out agent prior to isolation of the desired analyte using a tandem combination of prefilter material and extraction chromatographic resin. The method has been applied to the separation of individual analytes from spiked urine samples. Analytes were recovered in high yield and radionuclide purity with separation times as low as 30 min. The chemistry employed is compatible with automation on the ARSIIe instrument.

A method for the separation of beryllium from spectral interfering elements in inductively coupled plasma-atomic emission spectroscopic analysis.

A quick, simple and effective chromatographic method for the separation of beryllium from a wide range of elements is described. The elements selected comprise elements which can interfere with the determination of beryllium by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and elements which commonly occur in environmental and industrial sample matrices. Beryllium is separated from all possible ICP-AES spectral interfering elements using a single extraction chromatographic (EXC) cartridge containing an acidic chelating organophosphorus extractant, Dipex((R)), sorbed onto an inert polymeric substrate. The separation method has been evaluated using simulated samples generated using several different digestion methods currently employed in beryllium analyses performed in Department of Energy (DOE) facilities. Incorporating a guard cartridge containing either 2-ethyl-1-hexylphosphonic acid mono 2-ethyl-1-hexyl ester or bis(2,4,4-trimethylpentyl)phosphinic acid to selectively remove U(VI) allows the isolation of beryllium from samples containing over 100mg of uranium without changing the load, rinse or strip conditions of the method.

234Th analysis of marine sediments via extraction chromatography and liquid scintillation counting.

234Th is widely used as a natural tracer for study of biological mixing and particle scavenging processes in the ocean. This naturally occurring nuclide serves this purpose due to its convenient half-life (24.1 days), constant rate of production from 238U dissolved in seawater, and its strong tendency to attach to particles in seawater. As a beta/gamma emitter, 234Th may be determined using low-level gas-flow proportional counting, gamma spectrometry, and liquid scintillation counting (LSC). We describe here a technique which combines Cerenkov counting to evaluate 234Th (via 234Pa) with LSC alpha counting of 230Th added to the samples as a yield tracer. Our separation approach is based on a sample preparation procedure for marine sediments using nitric acid leaching in a "hot block", and extraction chromatography (TEVA x Resin) for Th isolation. Samples are counted in plastic LSC vials, using Ultima Gold AB cocktail, in 1 M H3PO4 media. A series of sediment samples spiked with known amounts of 234Th yielded activities within a few percent of the anticipated values.