Transport Of Actinides Research Articles

Diglycolamides as highly efficient carrier ligands for actinide transport in supported liquid membranes

Diglycolamides as highly efficient carrier ligands for actinide transport in supported liquid membranes

Microstructure of irradiated AGR TRISO particle buffer layers as measured by X-ray computed tomography

Shrinkage of the initially low-density buffer layer in tristructural isotropic (TRISO) coated fuel particles during irradiation is a well-known phenomenon with potential implications for fission product and actinide transport, as well as potential pyrocarbon fracture that in some cases has been observed to impact particle performance. During post-irradiation examination, the buffer layer's structure is commonly determined using 2D microscopy of a particle cross section or a series of particle cross sections at staggered depths. Although these methods provide a general idea of the irradiated buffer microstructure, they do not provide a full picture of the TRISO coating microstructure. By contrast, x-ray computed tomography (XCT) provides full 3D imaging of the TRISO particle. Particles from various compacts irradiated for the Advanced Gas Reactor Fuel Development and Qualification Program were imaged using XCT. Some of these particles were selected because of abnormal fission product inventories (e.g., low 137Cs), whereas others were randomly selected from the center of the fission product inventory distribution. Qualitative and quantitative analysis techniques were applied to the randomly selected particles as representatives of typical TRISO behavior to study the post-irradiation structure of the buffer layer. These results showed that, while separation of the buffer and inner pyrolytic carbon layers was a common behavior during the radiation-induced shrinkage of the buffer, a portion of the original buffer/inner pyrolytic carbon interface remained intact throughout irradiation in nearly all cases. These results also indicated clear trends in the degree of buffer densification with irradiation temperature and fluence.

Electronic Structures and Unusual Chemical Bonding in Actinyl Peroxide Dimers [An2O6]2+ and [(An2O6)(12-crown-4 ether)2]2+ (An = U, Np, and Pu).

As known, actinyl peroxides play important roles in environmental transport of actinides, and they have strategic importance in the application of nuclear industry. Compared to the most studied uranyl peroxides, the studies of transuranic counterparts are still few, and more information about these species is needed. In this work, experimentally inspired actinyl peroxide dimers ([An2O6]2+, An = U, Np, and Pu) have been studied and analyzed by using density functional theory and multireference wave function methods. This study determines that the three [An2O6]2+ have unique electronic structures and oxidation states, as [(UVIO2)2(O2)2-]2+, [(NpVIIO2)2(O2-)2]2+, and mixed-valent [(PuVI/VO2)2(O2)1-]2+. This study demonstrates the significance of two bridging oxo ligands with at most four electron holes availability in ionically directing actinyl and resulting in the unusual multiradical bonding in [(PuVI/VO2)2(O2)1-]2+. In addition, thermodynamically stable 12-crown-4 ether (12C4) chelated [(An2O6)(12C4)2]2+ complexes have been predicted, that could maintain these unique electronic structures of [An2O6]2+, where the An ← O12C4 dative bonding shows a trend in binding capacity of 12C4 from κ4 (U) to κ3 (Np) and κ4 (Pu). This study reveals the interesting electronic character and bonding feature of a series of early actinide elements in peroxide complexes, which can provide insights into the intrinsic stability of An-containing species.

Combining batch experiments and spectroscopy for realistic surface complexation modelling of the sorption of americium, curium, and europium onto muscovite

For a safe enclosure of contaminants, for instance in deep geological repositories of radioactive waste, any processes retarding metal migration are of paramount importance. This study focusses on the sorption of trivalent actinides (Am, Cm) and lanthanides (Eu) to the surface of muscovite, a mica and main component of most crystalline rocks (granites, granodiorites). Batch sorption experiments quantified the retention regarding parameters like pH (varied between 3 and 9), metal concentration (from 0.5 µM Cm to 10 µM Eu), or solid-to-liquid ratio (0.13 and 5.25 g·L−1). In addition, time-resolved laser fluorescence spectroscopy (TRLFS) using the actinide Cm(III) identified two distinct inner-sphere surface species. Combining both approaches allowed the development of a robust surface complexation model and the determination of stability constants of the spectroscopically identified species of (S-OH)2M3+ (logKo −8.89), (S-O)2M+ (logKo −4.11), and (S-O)2MOH (logKo −10.6), with all values extrapolated to infinite dilution. The inclusion of these stability constants into thermodynamic databases will improve the prognostic accuracy of lanthanide and actinide transport through groundwater channels in soils and crystalline rock systems.

Status report on AMS measurements of plutonium isotopes using the 1MV Tandetron Accelerator at IFIN-HH

Accelerator Mass Spectrometry is the most sensitive measurement method that allows us to determine 239, 240, and 244Pu radioisotopes in environmental samples with extremely low isotopic concentrations. By measuring plutonium isotopes, we focus our research activity on two main directions, monitoring of environmental nuclear pollution and nuclear astrophysics.This report gives an overview of the progress that was made in the determination of plutonium isotopes at IFIN-HH, and it starts with the studies performed for the transport and measurement of actinides using the 1MV Tandetron Accelerator. The 238U and 232Th isotopes were used as pilot beams for the determination of ion transport parameters, after which the isotopic ratios 239Pu/242Pu, 240Pu/242Pu, and 244Pu/242Pu were measured using the new Plutonium Standard ColPuS. The results obtained for the isotopic ratios agree with the consensus values of the standard. In addition, we developed radiochemical procedures for thorium, plutonium, and uranium separation, the chemical recoveries of uranium and thorium using UTEVA and TEVA resins are presented, where we used an Agilent ICP-MS system (Inductively Coupled Plasma Mass Spectrometry). The radiochemical separation is important mainly for obtaining target materials that can provide microscopic pilot beams as U and/or Th. Finally, a short overview is provided of the molecular interference challenges that are encountered when measuring plutonium isotopes.

Gaomiaozi bentonite colloids: Interactions with plutonium (IV) and zirconium (IV)

According to previous field experiments, carrier colloids represent the primary mechanism for enhancing the transport of actinides in the subsurface at former nuclear weapons facilities. However, sub-micrometer size investigations on the sorption/interactions between radionuclides and natural colloids are scarce. In the present study, interactions between Pu (IV)/Zr (IV) and the colloids formed from Chinese Gaomiaozi bentonite in water were evaluated using sorption experiments, scanning electron microscopy, transmission electron microscopy, dynamic light scattering, X-ray photoelectron spectroscopy, and small-angle X-ray scattering. Stable GMZ bentonite colloids showed zeta potentials of –31.8(0.9) mV at 25–85 ℃. Small-angle X-ray scattering from these colloids showed that the d-space (2.12 nm) of the colloidal particles dispersed in water exceeded that of mineral fragments obtained from the bulk powder (1.45 nm) in air, an indication of swelling. In addition, these colloidal particles (336 nm in size) exhibited higher affinities (Kd ~ 104 mL g−1) for Pu (IV) compared with bulk GMZ fragments (Kd ~ 103 mL g−1) at pH 7. X-ray diffraction showed that montmorillonite was the primarily component of colloidal GMZ particles, while X-ray photoelectron spectroscopy indicated that this clay mineral played an important role in the interaction with Pu (IV)/Zr (IV). Small-angle X-ray scattering from Zr (IV) solutions, showed power-law scattering (Intensity ∝ q−α) exponent α that increased from 2.6 to 3.4 (0.1 nm−1 <q < 0.5 nm−1), and decreased from 1.56 to 0.87 (q ~ 0.2 nm−1) as the Zr (IV) was raised from 0 to 9.8 × 10–11 mol dm–3. These results related to the partial agglomeration and precipitation of GMZ bentonite colloids. The remaining associative colloids pose a potential threat of Pu (IV) or Zr (IV) migration in subsurface waters.

Risk of colloidal and pseudo-colloidal transport of actinides in nitrate contaminated groundwater near a radioactive waste repository after bioremediation

The possible role of biogeochemical processes in the transport of colloidal and pseudo-colloidal U, Np, and Pu during bioremediation of radionuclide- and nitrate-contaminated groundwater was investigated. In two laboratory experiments with water samples taken from contaminated aquifers before and post bioremediation, we found that microbial processes could cause clayed, ferruginous, and actinide colloids to coagulate. The main mechanisms are biogenic insoluble ferrous iron species formations (goethite, pyrrhotite, siderite, troilite, and ferrihydrite), the aggregation of clay particles by microbial metabolites, and the immobilization of actinides in the bacterial cells, large polymers, and iron and clayed sediments. This process decreases the risk of colloidal and pseudo-colloidal transport of actinides.

Carrier mediated transport of actinides using hexa–n-hexylnitrilotriacetamide (HHNTA)

Solutions of N,N,N’,N’,N”,N”-hexa-n-hexylnitrilotriacetamide (HHNTA) in 20 % isodecanol-80 % n-dodecane (v/v) were employed for the supported liquid membrane (SLM) transport of U(VI), Np(IV), and Pu(IV) from nitric acid feed solutions using PTFE (polytetrafluoroethylene) flat sheet membranes. Preliminary transport studies revealed poor transport of U(VI) when compared with that of the tetravalent ions Np(IV) and Pu(IV) which may find application for their separation from acidic radioactive feeds. In view of this, all subsequent studies were carried out using Np(IV) and Pu(IV). The SLM studies performed with 0.08 M HHNTA as the carrier extractant indicated increased transport of the tetravalent actinide ions with increasing nitric acid and carrier extractant concentrations, while using 0.5 M HNO3 + 0.5 M oxalic acid as the strip (or receiver) phase composition. However, while > 80 % transport of Np(IV) and Pu(IV) was obtained for a feed phase of 3 M HNO3, a sharp decrease in the transport rate was seen at a feed acidity of 6 M HNO3 probably due to anionic hexanitrato complex formation of the metal ions and also because of lower availability of the free ligand in the membrane phase at higher nitric acid concentrations. The membrane stability was poor suggesting the need for continuous replenishment for long term use.

Characterizing the general chelating affinity of serum protein fetuin for lanthanides.

Fetuin is an abundant blood protein that participates in multiple biological processes, including the transport and regulation of calcium. Fetuin is also known to have a high affinity for uranium (as the uranyl dioxo cation) and plutonium, thus it has been suggested as one of the main endogenous chelating biomolecules involved in the transport of actinides following an internal uptake event. Nevertheless, no direct measurements of its affinity for f-elements beside these two actinides have been reported. Here, we investigate the interaction between fetuin and trivalent lanthanides, such as samarium, europium, terbium, and dysprosium, by mass spectrometry and fluorescence spectroscopy. Mass spectrometry results indicated that fetuin has four metal binding sites for the metal ions studied. Upon formation, the metal-protein complexes showed luminescence emission as a result of antenna sensitization of the metal ions, whose photophysics were characterized and exploited to perform direct spectrofluorimetric titrations. Furthermore, the thermodynamic constants were calculated for all complexes, confirming the formation of stable complexes with log [Formula: see text] values between 26 and 27. In characterizing the affinity of the serum protein fetuin for several f-elements, this study expands upon the initial findings focused on uranyl and plutonium, and contributes to a better understanding of the internal distribution and deposition of lanthanides, potentially representative of trivalent actinides.

Building [UIV 70 (OH)36 (O)64 ]4- Oxocluster Frameworks with Sulfate, Transition Metals, and UV.

Uranium(IV) oxide clusters, colloids, and materials are designed and studied for 1) nuclear materials applications, 2) understanding the environmental fate and transport of actinides, and 3) exploring the complex bonding behavior of open-shell f-elements. UIV -oxyhydroxsulfate clusters are particularly relevant in industrial processes and in nature. Recent studies have shown that counter-cations to these polynuclear anions differentiate rich structural topologies in the solid-state. Herein, we present nine different structures with wheel-shaped [U70 (OH)36 (O)64 (SO4 )60 ]4- (U70 ) linked into one- and two-dimensional frameworks with sulfate, divalent transition metals (CrII , FeII , CoII , NiII ) and UV . Small-angle X-ray scattering of these phases dissolved in butylamine reveals differing supramolecular assembly of U70 clusters, controlled primarily by sulfates. However, observed trends in transition metal linking guide future design of U70 materials with different topologies. Finally, U70 linking via UIV -O-UV -O-UIV bridges presents a rare example of mixed-oxidation-state uranium oxides without disorder.

Liquid-liquid extraction and facilitated transport of f-elements using an N-pivot tripodal ligand

Diglycolamide (DGA)-functionalized tripodal ligands offer the required nine-coordinated complex for effective binding to a trivalent lanthanide/actinide ion. A N-pivot tripodal ligand (TREN-DGA) containing three DGA pendant arms was evaluated for the extraction and supported liquid membrane transport studies using PTFE flat sheets. Solvent extraction studies indicated preferential extraction of 1:1 (M:L) species, while the metal ion extraction increased with increasing HNO3 concentration conforming to a solvated species extraction. Flat sheet-supported liquid membrane studies, carried out using 4.0 × 10−3 M TREN-DGA in 95% n-dodecane + 5% iso-decanol indicated faster mass transport for Eu3+ ion as compared to Am3+ ion. The determined transport parameters indicated slow diffusion of the M-TREN-DGA (M = Am or Eu) complex being the rate-determining step. The transport of lanthanides and actinides followed the trend: Eu3+ > Am3+∼ Pu4+ >> UO22+ and Am can be selectively separated from a mixture of U and Pu by oxidizing the latter to its +6 oxidation state. The liquid membrane stability was not encouraging and was deteriorating the transport efficiency with time, which was attributed to carrier loss into the aqueous phases.

Ab initio calculations of uranium and thorium storage in CaSiO3-perovskite in the Earth’s lower mantle

Earth’s mantle convection is powered in part by the radiogenic heat released by the decay of 238 U, 235 U, 232 Th, and 40 K. We present ab initio calculations of uranium and thorium incorporation in CaSiO 3 -perovskite with and without aluminum, and propose that aluminous calcium silicate perovskite is the likely host of uranium and thorium in the lower mantle. At 15 GPa, the enthalpies of solution into aluminum-free CaSiO 3 -perovskite are 10.34 kJ/mol for U 4+ and 12.52 kJ/mol for Th 4+ in SiO 2 saturated systems, while the enthalpies are 17.09 kJ/mol and 19.27 kJ/mol, respectively, in CaO saturated systems. Coupled substitution of U 4+ and Th 4+ with aluminum is thermodynamically favored, with the enthalpies of solution negative for U 4+ and near 0 kJ/mol for Th 4+ throughout the stability field of CaSiO 3 -perovskite. Therefore, U incorporation into CaSiO 3 -perovskite is spontaneous in the presence of aluminum while Th forms a near ideal solid solution, implying these elements are potentially compatible with respect to partial melting in the transition zone and lower mantle. Furthermore, the solid solution reactions of U 4+ and Th 4+ are broadly similar to each other, suggesting a restriction on the fractionation of these actinides between the upper and lower mantle. U and Th compatibility in the presence of Al has implications regarding actinide transport into the deep mantle within subducting slabs and the geochemical content of seismic anomalies at the core-mantle boundary.

Experimental evidence for ternary colloid-facilitated transport of Th(IV) with hematite (α-Fe2O3) colloids and Suwannee River fulvic acid

Previous field experiments have suggested colloid-facilitated transport via inorganic and organic colloids as the primary mechanism of enhanced actinide transport in the subsurface at former nuclear weapons facilities. In this work, research was guided by the hypothesis that humic substances can enhance tetravalent actinide (An(IV)) migration by coating and mobilizing natural colloids in environmental systems and increasing An(IV) sorption to colloids. This mechanism is expected to occur under relatively acidic conditions where organic matter can sorb and coat colloid surfaces and facilitate formation of ternary colloid-ligand-actinide complexes. The objective of this work was to examine Th transport through packed columns in the presence of hematite colloids and/or Suwannee River fulvic acid (SRFA). In the presence of SRFA, with or without hematite colloids, significant transport (>60% recovery within the effluent) of thorium occurred through quartz columns. It is notable that the SRFA contributed to increased transport of both Th and hematite colloids, while insignificant transport occurred in the absence of fulvic acid. Further, in the presence of a natural sandy sediment (as opposed to pure quartz), transport is negligible in the presence of SRFA due to interactions with natural, clay-sized sediment coatings. Moreover, this data shows that the transport of Th through quartz columns is enhanced in ternary Th-colloid-SRFA and binary Th-SRFA systems as compared to a system containing only Th.

Influence of the goethite (α-FeOOH) surface on the stability of distorted PuO2 and PuO2–x phases

Abstract Experiments by [Powell, B. A., Dai, Z. R., Zavarin, M., Zhao, P. H., Kersting, A. B.: Stabilization of plutonium nano-colloids by epitaxial distortion on mineral surfaces. Environ. Sci. Technol. 45, 2698 (2011).] deduced the heteroepitaxial growth of a bcc Pu4O7 phase when sorbed onto goethite from d-spacing measurements obtained from selected-area electron diffraction (SAED) patterns. The structural and/or chemical modification of Pu(IV) oxide (PO) nanocolloids upon sorption to goethite, in turn, affects colloidal-transport of Pu in the subsurface. In this study, molecular simulations were applied to investigate mechanisms affecting the formation of non-fcc PO phases and to understand the influence of goethite in stabilizing the non-fcc PO phase. Analyses of the structure, chemistry, and formation energetics for several bulk PuO2 and PuO2–x phases, using ab initio methods, show that the formation of a non-fcc PO can occur from the lattice distortion (LD) of fcc PuO2 upon sorption and formation of a PO–goethite interface. To strain and non-uniformly distort the PuO2 lattice to match that of the goethite substrate at ambient conditions would require 88 kJ/mol Pu4O8. The formation of a hypostoichiometric PuO2–x phase, such as the experimentally-deduced bcc, Ia3̅ Pu4O7 phase, requires more O-poor conditions and/or high energetic inputs (&gt; +365 kJ/mol Pu4O7 at O-rich conditions). Empirical methods were also applied to study the effect of lattice distortion on sorption energetics and adsorbate particle growth using simple heterointerfaces between cubic salts, where KCl clusters (notated as KClLD) of varying size and lattice mismatch (LM) were sorbed to a NaCl cluster. When the lattice of a KClLD cluster has &lt;15% LM with that of a NaCl substrate, the sorption of KClLD onto NaCl is exothermic (&lt;–80 kJ/mol) and the KClLD cluster can reach sizes of ~2–5 nm on the NaCl substrate. These models suggest that the lattice of a fcc PuO2 particle can distort upon formation of a heterointerface with goethite to lower LM, in turn better enabling the growth of the PO adsorbates and yielding more exothermic adsorption energies. A more detailed understanding of the interfacial environment between PO and goethite is obtained through structural, chemical, and energetic analyses on modeled PuO2 (110)– and PuO2–x (110)–goethite (001) heterointerfaces. Structural analyses of the heterointerfaces continue to support that the lattice of PO is strained to better match that of goethite and thus lead to the formation of a non-fcc PO phase. When the lattice of the PO (110) surface is distorted to match that of the goethite (001) surface, the alignment and d-spacings from simulated electron diffraction patterns for the PO–goethite heterointerfaces reproduce experimental observations. Non-fcc PO thin-films are also found to be stabilized through the formation of an interface with goethite, as the work of adhesion for the PuO2– and PuO2–x–goethite interfaces are 1.4 J/m2 and 2.0 J/m2, respectively. Analyses of electron and charge density of the heterointerfaces also show that covalent- to polar-covalent bonding at the interface promotes the stabilization of a PO–goethite interface. The results from these models contribute to experimental observations, providing further understanding of how the goethite substrate influences the formation and stabilization of a non-fcc PO phase. Furthermore, the information from this study aids in better understanding processes at mineral–water interfaces that influence actinide transport.

Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing

Nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. We find significant variations among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. The resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.

Decreased Salinity and Actinide Mobility: Colloid-Facilitated Transport or pH Change?

Colloids have been implicated in influencing the transport of actinides and other adsorbed contaminants in the subsurface, significantly increasing their mobility. Such colloid-facilitated transport can be induced by changes in groundwater chemistry that occur, for example, when high ionic strength contaminant plumes are displaced by infiltrating rainwater. We studied the transport and mobility of Th(IV), as an analogue for Pu(IV) and other tetravalent actinides [An(IV)], in saturated columns packed with a natural heterogeneous subsurface sandy sediment. As expected, decreases in ionic strength both promoted the mobilization of natural colloids and enhanced the transport of previously adsorbed Th(IV). However, colloid-facilitated transport played only a minor role in enhancing the transport of Th(IV). Instead, the enhanced transport of Th(IV) was primarily due to the pH-dependent desorption of Th(IV) caused by the change in ionic strength. In contrast, the adsorption of Th(IV) had a marked impact on the surface charge of the sandy sediment, significantly affecting the mobility of the colloids. In the absence of Th(IV), changes in ionic strength were ineffective at releasing colloids while in the presence of Th(IV), decreases in ionic strength liberated significant concentrations of colloids. Therefore, under the conditions of our experiments which mimicked acidic, high ionic strength groundwater contaminant plumes, Th(IV) had a much greater effect on colloid transport than colloids had on Th(IV) transport.

Francis P. Garvan-John M. Olin Medal: Annie Kersting

AWARDS Francis P. Garvan-John M. Olin Medal: Annie Kersting ShareShare onFacebookTwitterWechatLinked InRedditEmail C&EN, 2016, 94 (1), pp 38–43January 4, 2016Cite this:C&EN 94, 1, 38-43Figure1of1Sponsor: Francis P. Garvan-John M. Olin Medal Endowment Citation: For seminal contributions to understanding radionuclide behavior in the environment, mentoring students and postdocs, and developing successful education programs in nuclear forensics and environmental radiochemistry. Current position: director, Glenn T. Seaborg Institute, Lawrence Livermore National Laboratory Education: B.A., geology and geophysics, University of California, Berkeley; M.S., Ph.D., geology and geophysics, University of Michigan, Ann Arbor Kersting on her role model:“One of my favorite role models is Marie Curie. She was an amazing woman, and is an inspiration to many scientists, not just women scientists. She was a brilliantly creative scientist, who, through her accomplishments, broke down many barriers for women and made it possible for my generation to have opportunities in science. Her accomplishments were far reaching. She was the first woman to receive a Nobel Prize; she was the first scientist to win two Nobel Prizes; and she also was the first person to win two Nobel Prizes in two different fields, chemistry and physics. Through her accomplishments, she showed us that gender should not limit one’s ability to achieve. She was fearless in her pursuit of scientific discovery; her life has inspired many.” What her colleagues say:“Dr. Annie Kersting is internationally recognized for research on the fate and transport of plutonium and other actinides in the environment. Her research has transformed our fundamental chemical understanding of migration of plutonium and other contaminants in the biosphere. Specifically, she showed in her seminal paper (Nature 1999, DOI: 10.1038/16231) that plutonium is not immobilized as originally thought, but can be transported on small particulates or colloids.”—Darleane Hoffman, University of California, Berkeley

Siderocalin-mediated recognition, sensitization, and cellular uptake of actinides

Synthetic radionuclides, such as the transuranic actinides plutonium, americium, and curium, present severe health threats as contaminants, and understanding the scope of the biochemical interactions involved in actinide transport is instrumental in managing human contamination. Here we show that siderocalin, a mammalian siderophore-binding protein from the lipocalin family, specifically binds lanthanide and actinide complexes through molecular recognition of the ligands chelating the metal ions. Using crystallography, we structurally characterized the resulting siderocalin-transuranic actinide complexes, providing unprecedented insights into the biological coordination of heavy radioelements. In controlled in vitro assays, we found that intracellular plutonium uptake can occur through siderocalin-mediated endocytosis. We also demonstrated that siderocalin can act as a synergistic antenna to sensitize the luminescence of trivalent lanthanide and actinide ions in ternary protein-ligand complexes, dramatically increasing the brightness and efficiency of intramolecular energy transfer processes that give rise to metal luminescence. Our results identify siderocalin as a potential player in the biological trafficking of f elements, but through a secondary ligand-based metal sequestration mechanism. Beyond elucidating contamination pathways, this work is a starting point for the design of two-stage biomimetic platforms for photoluminescence, separation, and transport applications.

Experimental and Theoretical Studies of Actinide and Lanthanide Ion Transport Across Supported Liquid Membranes

In this work, we propose a new transport mechanism for metal ions relevant for used nuclear fuel separation processes by a supported liquid membrane (SLM). Two SLM extraction systems were investigated where the membrane was impregnated with either di-(2-ethylhexyl)phosphoric acid (HDEHP) or tributyl phosphate (TBP). A HDEHP impregnated membrane was used to extract neodymium (III), representative of a typical trivalent lanthanide. Cerium, which was oxidized by sodium bismuthate from trivalent to tetravalent state, was extracted by TBP. Oxidized cerium was used as a surrogate for oxidized americium to investigate the kinetics and possibility of americium and curium separation by membrane extraction. Both extraction systems were operated at varying nitric acid concentrations, and changes in the kinetics and extraction efficiency of metal ions were investigated. The proposed transport mechanism that was chosen for our studies was modified from the previous works by Danesi et al.[1,2] and Cussler et al.[3] The mechanism was selected due to the ability to accommodate and describe transport phenomena across a SLM when formation of extractant nano-channels in the membrane may exist. We were able to obtain acceptable fit of the models to our overall data trends although chemical and physical conditions must be well established and purity and homogeneity of the membrane are critical. A reverse transport of metal ions was observed when leaving the system for longer times which agrees with our model. The membrane was investigated for degradation and shown to be stable after contact with up to 7 M nitric acid for over 2000 minutes. Finally, we examined the possibility of partitioning americium from curium using a SLM impregnated by TBP. Separation of americium from curium was observed although not to a degree that was expected based on the Ce(IV) transport. Incomplete oxidation of Am(III) to Am(V) and reduction of Am(VI) on the membrane surface are possible causes for this observed discrepancy. Our model was, however, able to accurately predict Cm(III) transport through the membrane.

Mechanical environmental transport of actinides and 137Cs from an arid radioactive waste disposal site

Aeolian and pluvial processes represent important mechanisms for the movement of actinides and fission products at the Earth's surface. Soil samples taken in the early 1970's near a Department of Energy radioactive waste disposal site (the Subsurface Disposal Area, SDA, located in southeastern Idaho) provide a case study for studying the mechanisms and characteristics of environmental actinide and 137Cs transport in an arid environment. Multi-component mixing models suggest actinide contamination within 2.5 km of the SDA can be described by mixing between 2 distinct SDA end members and regional nuclear weapons fallout. The absence of chemical fractionation between 241Am and 239+240Pu with depth for samples beyond the northeastern corner and lack of 241Am in-growth over time (due to 241Pu decay) suggest mechanical transport and mixing of discrete contaminated particles under arid conditions. Occasional samples northeast of the SDA (the direction of the prevailing winds) contain anomalously high concentrations of Pu with 240Pu/239Pu isotopic ratios statistically identical to those in the northeastern corner. Taken together, these data suggest flooding resulted in mechanical transport of contaminated particles into the area between the SDA and a flood containment dike in the northeastern corner, following which subsequent contamination spreading in the northeastern direction resulted from wind transport of discrete particles.