Anthropogenic plutonium-244 in the environment: Insights into plutonium's longest-lived isotope.

Owing to the rich history of heavy element production in the unique high flux reactors that operated at the Savannah River Site, USA (SRS) decades ago, trace quantities of plutonium with highly unique isotopic characteristics still persist today in the SRS terrestrial environment. Development of an effective sampling, processing, and analysis strategy enables detailed monitoring of the SRS environment, revealing plutonium isotopic compositions, e.g., (244)Pu, that reflect the unique legacy of plutonium production at SRS. This work describes the first long-term investigation of anthropogenic (244)Pu occurrence in the environment. Environmental samples, consisting of collected foot borne debris, were taken at SRS over an eleven year period, from 2003 to 2014. Separation and purification of trace plutonium was carried out followed by three stage thermal ionization mass spectrometry (3STIMS) measurements for plutonium isotopic content and isotopic ratios. Significant (244)Pu was measured in all of the years sampled with the highest amount observed in 2003. The (244)Pu content, in femtograms (fg = 10(-15) g) per gram, ranged from 0.31 fg/g to 44 fg/g in years 2006 and 2003 respectively. In all years, the (244)Pu/(239)Pu atom ratios were significantly higher than global fallout, ranging from 0.003 to 0.698 in years 2014 and 2003 respectively.

Plutonium isotopes in the terrestrial environment at the Savannah River Site, USA: a long-term study.

This work presents the findings of a long-term plutonium (Pu) study at Savannah River Site (SRS) conducted between 2003 and 2013. Terrestrial environmental samples were obtained at the Savannah River National Laboratory (SRNL) in the A-Area. Plutonium content and isotopic abundances were measured over this time period by α particle and thermal ionization mass spectrometry (3STIMS). We detail the complete process of the sample collection, radiochemical separation, and measurement procedure specifically targeted to trace plutonium in bulk environmental samples. Total plutonium activities were determined to be not significantly above atmospheric global fallout. However, the (238)Pu/(239+240)Pu activity ratios attributed to SRS are substantially different than fallout due to past (238)Pu production on the site. The (240)Pu/(239)Pu atom ratios are reasonably consistent from year to year and are lower than fallout indicating an admixture of weapons-grade material, while the (242)Pu/(239)Pu atom ratios are higher than fallout values, again due to actinide production activities. Overall, the plutonium signatures obtained in this study reflect a distinctive mixture of weapons-grade, heat source, and higher burn-up plutonium with fallout material. This study provides a unique opportunity for developing and demonstrating a blue print for long-term low-level monitoring of trace plutonium in the environment.

Effect of fulvic acid on neodymium uptake by goethite.

Experimental studies of the interaction of aqueous neodymium (Nd), Suwannee River fulvic acid (FA), and solid phase goethite were conducted. Results from blank systems (individual Nd and FA), binary systems (Nd-goethite, FA-goethite, and Nd-FA), and ternary systems (Nd-FA-goethite) at 0.1 mol/kg and 25°C are reported. In the binary Nd-goethite system a classic sorption edge is observed, whereby virtually all Nd is removed from solution above the goethite point of zero charge (PZC). Similarly, the binary FA-goethite system exhibits strong FA sorption; However in this system near complete removal of FA from solution is observed below the goethite PZC. In the binary Nd-FA system, both aqueous Nd and FA feature a sharp decrease in concentration at ca. pH 9. Various experiments in the ternary system were conducted. For all concentrations, FA enhanced Nd sorption below the goethite PZC, attributed to the formation of a Type B ternary surface complex (mineral-ligand-metal ion). Notably, the 100 ppm FA ternary system showed anomalously high dissolved Nd in solution above the PZC (i.e., Nd sorption suppression) and a concomitant increase in goethite dissolution (∼9 ppm total Fe(3+) observed above circa pH 9.5). Our results suggest that Nd-FA complexation plays a key role in Nd uptake by goethite, and that this process is largely governed by pH: Whereas at pHs below the goethite PZC, Nd-FA complexation facilitates Nd sorption, above the PZC, and particularly at elevated FA concentrations, the formation of aqueous Nd-FA complexes suppresses Nd removal. Moreover, under these conditions, goethite dissolution may also play a role in mitigating Nd uptake by goethite.

Uranyl peroxide enhanced nuclear fuel corrosion in seawater.

The Fukushima-Daiichi nuclear accident brought together compromised irradiated fuel and large amounts of seawater in a high radiation field. Based on newly acquired thermochemical data for a series of uranyl peroxide compounds containing charge-balancing alkali cations, here we show that nanoscale cage clusters containing as many as 60 uranyl ions, bonded through peroxide and hydroxide bridges, are likely to form in solution or as precipitates under such conditions. These species will enhance the corrosion of the damaged fuel and, being thermodynamically stable and kinetically persistent in the absence of peroxide, they can potentially transport uranium over long distances.

Energetics of Al13 Keggin cluster compounds.

The ε-Al(13) Keggin aluminum hydroxide clusters are essential models in establishing molecular pathways for geochemical reactions. Enthalpies of formation are reported for two salts of aluminum centered ε-Keggin clusters, Al(13) selenate, (Na(AlO(4))Al(12)(OH)(24)(SeO(4))(4)•12H(2)O) and Al(13) sulfate, (NaAlO(4)Al(12)(OH)(24)(SO(4))(4)•12H(2)O). The measured enthalpies of solution, ΔH(sol), at 28 °C in 5 N HCl for the ε-Al(13) selenate and sulfate are -924.57 (± 3.83) and -944.30 ( ± 5.66) kJ·mol(-1), respectively. The enthalpies of formation from the elements, ΔH(f,el), for Al(13) selenate and sulfate are -19,656.35 ( ± 67.30) kJ·mol(-1), and -20,892.39 ( ± 70.01) kJ·mol(-1), respectively. In addition, ΔH(f,el) for sodium selenate decahydrate was calculated using data from high temperature oxide melt solution calorimetry measurements: -4,006.39 ( ± 11.91) kJ·mol(-1). The formation of both ε-Al(13) Keggin cluster compounds is exothermic from oxide-based components but energetically unfavorable with respect to a gibbsite-based assemblage. To understand the relative affinity of the ε-Keggin clusters for selenate and sulfate, the enthalpy associated with two S-Se exchange reactions was calculated. In the solid state, selenium is favored in the Al(13) compound relative to the binary chalcogenate, while in 5 N HCl, sulfur is energetically favored in the cluster compound compared to the aqueous solution. This contribution represents the first thermodynamic study of ε-Al(13) cluster compounds and establishes a method for other such molecules, including the substituted versions that have been created for kinetic studies. Underscoring the importance of ε-Al(13) clusters in natural and anthropogenic systems, these data provide conclusive thermodynamic evidence that the Al(13) Keggin cluster is a crucial intermediate species in the formation pathway from aqueous aluminum monomers to aluminum hydroxide precipitates.