Jon M. Schwantes

Collection of Lanthanides and Actinides from Natural Waters with Conventional and Nanoporous Sorbents

Effective collection of trace-level lanthanides and actinides is advantageous for recovery and recycling of valuable resources, environmental remediation, chemical separations, and in situ monitoring. Using isotopic tracers, we have evaluated a number of conventional and nanoporous sorbent materials for their ability to capture and remove selected lanthanides (Ce and Eu) and actinides (Th, Pa, U, and Np) from fresh and salt water systems. In general, the nanostructured materials demonstrated a higher level of performance and consistency. Nanoporous silica surface modified with 3,4-hydroxypyridinone provided excellent collection and consistency in both river water and seawater. The MnO(2) materials, in particular the high surface area small particle material, also demonstrated good performance. Other conventional sorbents typically performed at levels below the nanostructured sorbents and demonstrate a larger variability and matrix dependency.

Nuclear archeology in a bottle: evidence of pre-Trinity U.S. weapons activities from a waste burial site.

During World War II, the Hanford Site in Washington became the location for U.S. plutonium production. In 2004, a bottle containing a sample of plutonium was recovered from a Hanford waste trench. Here, state-of-the-art instrumental analyses, reactor model simulations, and investigative science techniques were used to provide insights as to the origin of this unknown sample, a process collectively termed as nuclear archeology. Isotopic age dating conducted on the sample in 2007 indicated the sample was separated from the spent fuel 61.6 +/- 4.5 years earlier. The isotope (22)Na, a detectable product of a secondary nuclear reaction, proved useful as a powerful tool for nuclear forensic analysis as (1) an easily detectable signifier of the presence of alpha emitting actinides, (2) an indicator of sample splitting, and (3) a measure of the time since sample splitting. Analytical results of minor actinide isotopes and reactor model simulations confirmed the material originated from the X-10 reactor in Oak Ridge, TN. Corroborated by historical documents, we concluded this sample was part of the first batch of Pu separated at T-Plant, Hanford, the worlds first industrial-scale reprocessing facility, on December 9, 1944. This sample represents the oldest known collection of man-made (239)Pu in the world.

Investigation of the polymorphs and hydrolysis of uranium trioxide

This work focuses on the polymorphic nature of the UO3 and UO3–H2O system, which are important materials associated with the nuclear fuel cycle. The UO3–water system is complex and has not been fully characterized, even though these species are key fuel cycle materials. Powder X-ray diffraction, and Raman and fluorescence spectroscopies were used to characterize both the several polymorphic forms of UO3 and the certain UO3-hydrolysis products for the purpose of developing predictive capabilities and estimating process history; for example, polymorphic phases of unknown origin. Specifically, we have investigated three industrially relevant production pathways of UO3 and discovered a previously unknown low temperature route to the production of β-UO3. Several phases of UO3, its hydrolysis products, and key starting materials were synthesized and characterized as pure materials to establish optical spectroscopic signatures for these compounds for forensic analysis.

Extraction of short-lived zirconium and hafnium isotopes using crown ethers: A model system for the study of rutherfordium

Summary The extraction of zirconium and hafnium from hydrochloric acid media was studied using the crown ethers dibenzo-18-crown-6 (DB18C6), dicyclohexano-18-crown-6 (DC18C6) and dicyclohexano-24-crown-8 (DC24C8) as extractants. The goal was to find an extraction system that exhibits a high selectivity between the members of group 4 of the periodic table and is suitable for the study of rutherfordium. It was found that Zr and Hf are both extracted using DB18C6, DC18C6 and DC24C8. The extraction yield increases with increasing acid concentration and increasing concentration of crown ether. The extracted species most likely consists of an ion-association complex formed between a Zr or Hf chloro complex and a hydronium crown ether complex. Conditions can be found for each extractant that provide for the separation of Zr from Hf. This selective separation between Zr and Hf makes the extraction with crown ethers from HCl well suited to study the extraction behaviour of Rf and compare it to the behaviour of Zr and Hf. These extraction systems can be used to determine whether the extraction behaviour of Rf is similar to Zr, similar to Hf or follows the trend established by the lighter homologs. The extraction kinetics are fast enough for the study of the 78-s isotope 261mRf.

Collection of fission and activation product elements from fresh and ocean waters: A comparison of traditional and novel sorbents

Monitoring natural waters for the inadvertent release of radioactive fission products produced as a result of nuclear power generation downstream from these facilities is essential for maintaining water quality. To this end, we evaluated sorbents for simultaneous in-situ large volume extraction of radionuclides with both soft (e.g., Ag) and hard metal (e.g., Co, Zr, Nb, Ba, and Cs) or anionic (e.g., Ru, Te, Sb) character. In this study, we evaluated a number of conventional and novel nanoporous sorbents in both fresh and salt waters. In most cases, the nanoporous sorbents demonstrated enhanced retention of analytes. Salinity had significant effects upon sorbent performance and was most significant for hard cations, specifically Cs and Ba. The presence of natural organic matter had little effect on the ability of chemisorbents to extract target elements.

Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly

Assembly of a family of 12 supramolecular compounds containing [AnO2Cl4]2- (An = U, Np, Pu), via hydrogen and halogen bonds donated by substituted 4-X-pyridinium cations (X = H, Cl, Br, I), is reported. These materials were prepared from a room-temperature synthesis wherein crystallization of unhydrolyzed and valence-pure [An(VI)O2Cl4]2- (An = U, Np, Pu) tectons is the norm. We present a hierarchy of assembly criteria based on crystallographic observations and subsequently quantify the strengths of the non-covalent interactions using Kohn-Sham density functional calculations. We provide, for the first time, a detailed description of the electrostatic potentials of the actinyl tetrahalide dianions and reconcile crystallographically observed structural motifs and non-covalent interaction acceptor-donor pairings. Our findings indicate that the average electrostatic potential across the halogen ligands (the acceptors) changes by only ∼2 kJ mol-1 across the AnO22+ series, indicating that the magnitude of the potential is independent of the metal center. The role of the cation is therefore critical in directing structural motifs and dictating the resulting hydrogen and halogen bond strengths, the former being stronger due to the positive charge centralized on the pyridyl nitrogen, N-H+. Subsequent analyses using the quantum theory of atoms in molecules and natural bond orbital approaches support this conclusion and highlight the structure-directing role of the cations. Whereas one can infer that Columbic attraction is the driver for assembly, the contribution of the non-covalent interaction is to direct the molecular-level arrangement (or disposition) of the tectons.

Mechanisms of plutonium sorption to mineral oxide surfaces: new insights with implications for colloid-enhanced migration

Abstract New equilibrium and kinetic models have been developed to describe rate-limited sorption and desorption of Pu onto and off of mineral oxide surfaces using a generic approach to estimate sorption constants that require minimal laboratory calibrations. Equilibrium reactions describing a total of six surface species were derived from a combination of empirical relationships previously described in the literature and generated as part of this work. These sorption reactions and corresponding equilibrium constants onto goethite (and silica) are: ≡SOH + Pu3+ ↔ ≡SOPu2+ + H+, logߙK = −2.1(−10)  (1) ≡SOH + Pu4+ ↔ ≡SOPu3+ + H+, logߙK = 15.3(7.2)  (2) ≡SOH + PuO2+ ↔ ≡SOPuO2 + H+, logߙK = −8.5(−16.5)  (3) ≡SOH + PuO22+ ↔ ≡SOPuO2+ + H+, logߙK = 1.2(−6.5)  (4) ≡SOH + Pu4+ + 3H2O ↔ ≡SOPu(OH)3 + 4H+, logߙK = 12.5(4.6)  (5) ≡SOH + Pu4+ + 4H2O ↔ ≡SOPu(OH)4− + 5H+, logߙK = 5.0(−2.3)  (6) The kinetic model decouples reduced (III, IV) and oxidized (V, VI) forms of Pu via a single rate-limiting, but reversible, surface mediated reaction:...

Optimization and evaluation of mixed-bed chemisorbents for extracting fission and activation products from marine and fresh waters

Chemically selective chemisorbents are needed to monitor natural and engineered waters for anthropogenic releases of stable and radioactive contaminants. Here, a number of individual and mixtures of chemisorbents were investigated for their ability to extract select fission and activation product elements from marine and coastal waters, including Co, Zr, Ru, Ag, Te, Sb, Ba, Cs, Ce, Eu, Pa, Np, and Th. Conventional manganese oxide and cyanoferrate sorbents, including commercially available Anfezh and potassium hexacyanocobalt(II) ferrate(II) (KCFC), were tested along with novel nano-structured surfaces (known as Self Assembled Monolayers on Mesoporous Supports or SAMMS) functionalized with a variety of moieties including thiol, diphosphonic acid (DiPhos-), methyl-3,4 hydroxypyridinone (HOPO-), and cyanoferrate. Extraction efficiencies were measured as a function of salinity, organic content, temperature, flow rate and sample size for both synthetic and natural fresh and saline waters under a range of environmentally relevant conditions. The effect of flow rate on extraction efficiency, from 1 to 70 mL min(-1), provided some insight on rate limitations of mechanisms affecting sorption processes. Optimized mixtures of sorbent-ligand chemistries afforded excellent retention of all target elements, except, Ba and Sb. Mixtures of tested chemisorbents, including MnO(2)/Anfezh and MnO(2)/KCFC/Thiol (1-3 mm)-SAMMS, extracted 8 of the 11 target elements studied to better than 80% efficiency, while a mixture of MnO(2)/Anfezh/Thiol (75-150 μm)-SAMMS mixture was able to extract 7 of the 11 target elements to better than 90%. Results generated here indicate that flow rate should be less of a consideration for experimental design if sampling from fresh water containing variable amounts of DOM, rather than collecting samples from salt water environments. Relative to the capability of any single type of chemisorbent tested, optimized mixtures of several sorbents are able to increase the number of elements that can be efficiently and simultaneously extracted from natural waters.

Fourth Collaborative Materials Exercise of the Nuclear Forensics International Technical Working Group

The Nuclear Forensics International Technical Working Group is a community of nuclear forensic practitioners who respond to incidents involving nuclear and other radioactive material out of regulatory control. The Group is dedicated to advancing nuclear forensic science in part through periodic participation in materials exercises. The Group completed its fourth Collaborative Materials Exercise in 2015 in which laboratories from 15 countries and one multinational organization analyzed three samples of special nuclear material in support of a mock nuclear forensic investigation. This special section of the Journal for Radioanalytical and Nuclear Chemistry is devoted to summarizing highlights from this exercise.

Structure and Bonding Investigation of Plutonium Peroxocarbonate Complexes Using Cerium Surrogates and Electronic Structure Modeling

Herein, we report the synthesis and structural characterization of K8[(CO3)3Pu]2(μ-η2-η2-O2)2·12H2O. This is the second Pu-containing addition to the previously studied alkali-metal peroxocarbonate series M8[(CO3)3A]2(μ-η2-η2-O2)2·xH2O (M = alkali metal; A = Ce or Pu; x = 8, 10, 12, or 18), for which only the M = Na analogue has been previously reported when A = Pu. The previously reported crystal structure for Na8[(CO3)3Pu]2(μ-η2-η2-O2)2·12H2O is not isomorphous with its known Ce analogue. However, a new synthetic route to these M8[(CO3)3A]2(μ-η2-η2-O2)2·12H2O complexes, described below, has produced crystals of Na8[(CO3)3Ce]2(μ-η2-η2-O2)2·12H2O that are isomorphous with the previously reported Pu analogue. Via this synthetic method, the M = Na, K, Rb, and Cs salts of M8[(CO3)3Ce]2(μ-η2-η2-O2)2·xH2O have also been synthesized for a systematic structural comparison with each other and the available Pu analogues using single-crystal X-ray diffraction, Raman spectroscopy, and density functional theory calculations. The Ce salts, in particular, demonstrate subtle differences in the peroxide bond lengths, which correlate with Raman shifts for the peroxide Op-Op stretch (Op = O atoms of the peroxide bridges) with each of the cations studied: Na+ [1.492(3) Å/847 cm-1], Rb+ [1.471(1) Å/854 cm-1], Cs+ [1.474(1) Å/859 cm-1], and K+ [1.468(6) Å/870 cm-1]. The trends observed in the Op-Op bond distances appear to relate to supermolecular interactions between the neighboring cations.