A Novel Method for Tracer Concentration Plutonium(V) Solution Preparation.

Preparation of relatively pure low concentration Pu(V) solutions for environmental studies is nontrivial due to the complex redox chemistry of Pu. Ozone gas generated by an inexpensive unit designed for household-use was used to oxidize a 2 × 10(-8) M Pu(IV) solution to predominantly Pu(VI) with some Pu(V) present. Over several days, the Pu(VI) in the solution reduced to Pu(V) without further reducing to Pu(IV). The reduction from Pu(VI) to Pu(V) could be accelerated by raising the pH of the solution, which led to an immediate conversion without substantial conversion to Pu(IV). The aqueous Pu was found to be stable as predominately Pu(V) for greater than one month from pH 3-7; however, at circumneutral pH, a sizable fraction of Pu was lost from solution by either precipitation or sorption to the vial walls. This method provides a fast means of preparing Pu(V) solutions for tracer concentration studies without numerous extraction or cleanup steps.

Effects of Titanium Doping in Titanomagnetite on Neptunium Sorption and Speciation.

Neptunium-237 is a radionuclide of great interest owing to its long half-life (2.14 × 10(6) years) and relative mobility as the neptunyl ion (NpO2(+)) under many surface and groundwater conditions. Reduction to tetravalent neptunium (Np(IV)) effectively immobilizes the actinide in many instances due to its low solubility and strong interactions with natural minerals. One such mineral that may facilitate the reduction of neptunium is magnetite (Fe(2+)Fe(3+)2O4). Natural magnetites often contain titanium impurities which have been shown to enhance radionuclide sorption via titanium's influence on the Fe(2+)/Fe(3+) ratio (R) in the absence of oxidation. Here, we provide evidence that Ti-substituted magnetite reduces neptunyl species to Np(IV). Titanium-substituted magnetite nanoparticles were synthesized and reacted with NpO2(+) under reducing conditions. Batch sorption experiments indicate that increasing Ti concentration results in higher Np sorption/reduction values at low pH. High-resolution transmission electron microscopy of the Ti-magnetite particles provides no evidence of NpO2 nanoparticle precipitation. Additionally, X-ray absorption spectroscopy confirms the nearly exclusive presence of Np(IV) on the titanomagnetite surface and provides supporting data indicating preferential binding of Np to terminal Ti-O sites as opposed to Fe-O sites.

Initial Benchmarking of the Liquid Sampling-Atmospheric Pressure Glow Discharge-Orbitrap System Against Traditional Atomic Mass Spectrometry Techniques for Nuclear Applications.

The integration of the liquid sampling-atmospheric pressure glow discharge (LS-APGD) ion source with Orbitrap mass spectrometers has resulted in new opportunities in the field of isotope ratio mass spectrometry. In a field that has been dominated by thermal ionization mass spectrometry (TIMS) and inductively coupled plasma mass spectrometry (ICP-MS) on quadrupole and scanning-mode sector field analyzer platforms for highly accurate and precise measurements, the LS-APGD-Orbitrap system offers a benchtop instrument capable of meeting the rigorous International Target Values for measurement uncertainty for uranium (U). In order to benchmark the LS-APGD-Orbitrap, a series of U certified reference materials with increasing 235U isotopic composition were analyzed. By using U samples ranging in enrichment from 1 to 80%, the ability of the system to measure isotope ratios over a wide range is demonstrated. This analysis represents the first time that the LS-APGD-Orbitrap system has been used to analyze highly enriched U samples, allowing for the measurement of each of the U isotopes, including 234U and 236U-related species, which had not been achieved previously. Ultimately, the LS-APGD-Orbitrap system was able to measure CRM U-800 (assayed as 235U / 238U = 4.265622) as 4.266922, with a combined uncertainty, (uc), of 0.040%. These results are compared to those obtained using traditional elemental mass spectrometers including TIMS and ICP-MS-based instruments. The effectiveness of the LS-APGD-Orbitrap MS system for measuring U isotopes shows excellent promise in nuclear forensics, safeguards, and other nuclear weapon-based applications. Graphical Abstract ᅟ.

Analysis of Rare Earth Elements in Uranium Using Handheld Laser-Induced Breakdown Spectroscopy (HH LIBS).

A portable handheld laser-induced breakdown spectroscopy (HH LIBS) instrument was evaluated as a rapid method to qualitatively analyze rare earth elements in a uranium oxide matrix. This research is motivated by the need for development of a method to perform rapid, at-line chemical analysis in a nuclear facility, particularly to provide a rapid first pass analysis to determine if additional actions or measurements are warranted. This will result in the minimization of handling and transport of radiological and nuclear material and subsequent exposure to their associated hazards. In this work, rare earth elements (Eu, Nd, and Yb) were quantitatively spiked into a uranium oxide powder and analyzed by the HH LIBS instrumentation. This method demonstrates the ability to rapidly identify elemental constituents in sub-percent levels in a uranium matrix. Preliminary limits of detection (LODs) were determined with values on the order of hundredths of a percent. Validity of this methodology was explored by employing a National Institute of Standards and Technology (NIST) standard reference materials (SRM) 610 and 612 (Trace Elements in Glass). It was determined that the HH LIBS method was able to clearly discern the rare earths elements of interest in the glass or uranium matrices.

Trace elemental analysis of bulk uranium materials using an inline automated sample preparation technique for ICP-OES.

An automated inline method for the separation of trace element impurities from uranium matrices using a 200 µL column packed with UTEVA resin is presented here utilizing an Elemental Scientific, Inc. prepFAST IC in combination with a Perkin Elmer Avio 500 ICP-OES. This method reduces human exposure to highly concentrated acids and uranium-rich samples by automating the chemistry and introduction to the ICP. Calibration standards were prepared using inline dilutions requiring a single stock standard. The separation of trace elements from uranium matrices requires samples to be prepared in 8 M HNO3, which can be detrimental to the ICP, thus a post-column dilution step was employed to dilute the eluent matrix to 4 M HNO3. The method was optimized for a sample-to-sample time of < 9 min and monitored 21 elements in total. Proof of concept experiments for 1 µg mL-1 trace elements spiked into 0.1 vol%, 0.5 vol%, and 1.0 vol% uranium matrices resulted in < 5% relative difference and < 10% relative standard deviation for triplicate measurements of each uranium matrix analyzed. Inline dilutions (pre-column) of 2 vol% uranium + 20 µg mL-1 trace elements resulted in accurate and precise measurements using dilution factors of 2×, 4×, 5×, and 20×. Method detection limits for the 21 elements (Al, B, Ba, Be, Cd, Ca, Co, Cu, Fe, Li, Pb, Mg, Mn, Ni, K, Sr, Na, V, Zn, Zr, and U) analyzed for ranged from 7 to 326 ng mL-1 for 70 µL volume injections.

An automated micro-separation system for the chromatographic removal of uranium matrix for trace element analysis by ICP-OES.

An automated, miniaturized, off-line separation technique is presented here using an Elemental Scientific Inc. microFAST MC system with UTEVA resin to extract the uranium matrix from its trace element impurities in aqueous media. The collected fractions were analyzed for ~ 30 trace elements using inductively coupled plasma - optical emission spectroscopy. Ten replicate samples were processed with a single column resulting in precision ranging from 3.3% to 6.2% relative standard deviation with regards to the trace element recoveries. Accuracy, with respect to trace element concentrations in the U3O8 Certified Reference Material 124-1, resulted in an average of 13.9% relative deviation while accuracy to the Canadian U3O8 reference material, CUP-2, resulted in an average relative deviation of 8.6%. The total separation time of this automated process was reduced to ~ 30 min per sample while employing a 0.5 mL UTEVA chromatographic resin bed and 2.5 mg of uranium.