Multiscale Speciation of U and Pu at Chernobyl, Hanford, Los Alamos, McGuire AFB, Mayak, and Rocky Flats.

The speciation of U and Pu in soil and concrete from Rocky Flats and in particles from soils from Chernobyl, Hanford, Los Alamos, and McGuire Air Force Base and bottom sediments from Mayak was determined by a combination of X-ray absorption fine structure (XAFS) spectroscopy and X-ray fluorescence (XRF) element maps. These experiments identify four types of speciation that sometimes may and other times do not exhibit an association with the source terms and histories of these samples: relatively well ordered PuO2+x and UO2+x that had equilibrated with O2 and H2O under both ambient conditions and in fires or explosions; instances of small, isolated particles of U as UO2+x, U3O8, and U(VI) species coexisting in close proximity after decades in the environment; alteration phases of uranyl with other elements including ones that would not have come from soils; and mononuclear Pu-O species and novel PuO2+x-type compounds incorporating additional elements that may have occurred because the Pu was exposed to extreme chemical conditions such as acidic solutions released directly into soil or concrete. Our results therefore directly demonstrate instances of novel complexity in the Å and µm-scale chemical speciation and reactivity of U and Pu in their initial formation and after environmental exposure as well as occasions of unexpected behavior in the reaction pathways over short geological but significant sociological times. They also show that incorporating the actual disposal and site conditions and resultant novel materials such as those reported here may be necessary to develop the most accurate predictive models for Pu and U in the environment.

Pu(iii) and Cm(iii) in the presence of EDTA: aqueous speciation, redox behavior, and the impact of Ca(ii).

The impact of calcium on the solubility, redox behavior, and speciation of the An(iii)-EDTA (An = Pu or Cm) system under reducing, anoxic conditions was investigated through batch solubility experiments, X-ray absorption spectroscopy (XAS), density functional theory (DFT), and time-resolved laser fluorescence spectroscopy (TRLFS). Batch solubility experiments were conducted from undersaturation using Pu(OH)3(am) as the solid phase in contact with 0.1 M NaCl-NaOH-HCl-EDTA-CaCl2 solutions at [EDTA] = 1 mM, pHm = 7.5-9.5, and [CaCl2] ≤20 mM. Additional samples targeted brine systems represented by 3.5 M CaCl2 and WIPP simulated brine. Solubility data in the absence of calcium were well-described by Pu(iii)-EDTA thermodynamic models, thus supporting the stabilization of Pu(iii)-EDTA complexes in solution. Cm(iii)-EDTA TRLFS data suggested the stepwise hydrolysis of An(iii)-EDTA complexes with increasing pH, and current Pu(iii)-EDTA solubility models were reassessed to evaluate the possibility of including Pu(iii)-OH-EDTA complexes and to calculate preliminary formation constants. Solubility data in the presence of calcium exhibited nearly constant log m(Pu)tot, as limited by total ligand concentration, with increasing [CaCl2]tot, which supports the formation of calcium-stabilized Pu(iii)-EDTA complexes in solution. XAS spectra without calcium showed partial oxidation of Pu(iii) to Pu(iv) in the aqueous phase, while calcium-containing experiments exhibited only Pu(iii), suggesting that Ca-Pu(iii)-EDTA complexes may stabilize Pu(iii) over short timeframes (t ≤45 days). DFT calculations on the Ca-Pu(iii)-EDTA system and TRLFS studies on the analogous Ca-Cm(iii)-EDTA system show that calcium likely stabilizes An(iii)-EDTA complexes but can also potentially stabilize An(iii)-OH-EDTA species in solution. This hints towards the possible existence of four major complex types within Ca-An(iii)-EDTA systems: An(iii)-EDTA, An(iii)-OH-EDTA, Ca-An(iii)-EDTA, and Ca-An(iii)-OH-EDTA. While the exact stoichiometry and degree of ligand protonation within these complexes remain undefined, their formation must be accounted for to properly assess the fate and transport of plutonium under conditions relevant to nuclear waste disposal.

Bacterial Pu(V) reduction in the absence and presence of Fe(III)-NTA: modeling and experimental approach.

Plutonium (Pu), a key contaminant at sites associated with the manufacture of nuclear weapons and with nuclear-energy wastes, can be precipitated to "immobilized" plutonium phases in systems that promote bioreduction. Ferric iron (Fe(3+)) is often present in contaminated sites, and its bioreduction to ferrous iron (Fe(2+)) may be involved in the reduction of Pu to forms that precipitate. Alternately, Pu can be reduced directly by the bacteria. Besides Fe, contaminated sites often contain strong complexing ligands, such as nitrilotriacetic acid (NTA). We used biogeochemical modeling to interpret the experimental fate of Pu in the absence and presence of ferric iron (Fe(3+)) and NTA under anaerobic conditions. In all cases, Shewanella alga BrY (S. alga) reduced Pu(V)(PuO(2) (+)) to Pu(III), and experimental evidence indicates that Pu(III) precipitated as PuPO(4(am).) In the absence of Fe(3+) and NTA, reduction of PuO(2) (+) was directly biotic, but modeling simulations support that PuO(2) (+) reduction in the presence of Fe(3+) and NTA was due to an abiotic stepwise reduction of PuO(2) (+) to Pu(4+), followed by reduction of Pu(4+) to Pu(3+), both through biogenically produced Fe(2+). This means that PuO(2) (+) reduction was slowed by first having Fe(3+) reduced to Fe(2+). Modeling results also show that the degree of PuPO(4(am)) precipitation depends on the NTA concentration. While precipitation out-competes complexation when NTA is present at the same or lower concentration than Pu, excess NTA can prevent precipitation of PuPO(4(am)).

Influence of ethylenediaminetetraacetic acid on the long-term oxidation state distribution of plutonium.

Spectrophotometry was used to study the effect of EDTA on plutonium oxidation state distribution as a function of time, pH, and ligand-to-metal ratio (L/M) under anoxic conditions. Novel Pu(V)-EDTA absorption bands were identified at 571, 993, 1105, and 1150 nm with molar absorption coefficients of 15 ± 1, 6 ± 1, 10 ± 1, and 10 ± 1 cm-1M-1, respectively. Pu(V)-EDTA spectral changes occurred at L/M < 1, indicating only PuVO2(EDTA)3- formed with logK = 3.6 ± 0.3. Time-resolved experiments showed EDTA drastically increased the Pu(V/VI) reduction rate, which we propose is driven by amine lone-pair electron donation and the oxidative decarboxylation of EDTA. Oxidation of Pu(III)-EDTA to Pu(IV)-EDTA occurred on a slower time scale (110-237 days) than previously reported (<15 min) and is hypothesized to be radiolysis driven. Pu(V/VI)-EDTA and Pu(III)-EDTA both approached Pu(IV)-EDTA stabilization over time, yet Pu(V/VI)-EDTA solubility data was ≥ 1.0 log10 units higher than predicted by Pu(IV)-EDTA solubility models, indicating that current thermodynamic models are incomplete. Ultimately, the data show EDTA preferentially stabilizes Pu(IV) over time regardless of initial oxidation state, but Pu(V)-EDTA can persist under environmentally-relevant conditions, emphasizing the need to continue investigating redox reactions, speciation, and behavior of these complexes to support the transuranic waste disposal and surface remediation/containment efforts.

Impact of Ca(II) on the aqueous speciation, redox behavior, and environmental mobility of Pu(IV) in the presence of EDTA.

The impact of calcium on the solubility and redox behavior of the Pu(IV)-EDTA system was investigated using a combination of undersaturation solubility studies and advanced spectroscopic techniques. Batch solubility experiments were conducted in 0.1 M NaCl-NaOH-HCl-EDTA-CaCl2 solutions at constant [EDTA] = 1∙10-3 M, 1 ≤ pHm ≤ 11, and 1∙10-3 M ≤ [CaCl2] ≤ 2∙10-2 M. Additional samples targeted brine systems represented by 3.5 M CaCl2 and WIPP simulated brine. Redox conditions were buffered with hydroquinone (pe + pH ≈ 9.5) with selected samples prepared in the absence of any redox buffer. All experiments were performed at T = 22 °C under Ar atmosphere. In-situ X-ray absorption spectroscopy indicated that PuO2(ncr,hyd) was the solubility-controlling phase during the lifetime of all experiments and that aqueous plutonium was present in the +IV oxidation state across all experimental conditions except at pHm ≈ 1, where a small fraction of Pu(III) was also identified. Current thermodynamic models overestimate Pu(IV)-EDTA solubility in the absence of calcium by approximately 1-1.5 log10-units and do not describe the nearly pH-independent, increased solubility observed with increased calcium concentrations. The ternary Pu(IV)-OH-EDTA system without calcium was reevaluated using solubility data obtained in this work and reported in the literature. An updated thermodynamic model including the complexes Pu(OH)(EDTA)-, Pu(OH)2(EDTA)2-, and Pu(OH)3(EDTA)3- was derived. Solubility data collected in the presence of calcium follows a pH-independent trend (log m(Pu)tot vs. pHm), which can only be explained by assuming the formation of a quaternary complex, tentatively defined as CaPu(OH)4(EDTA)2-, in solution. The significant enhancement of plutonium solubility observed in the investigated brine systems supports the formation of a quaternary complex that is not outcompeted by Ca(EDTA)2-, even in concentrated CaCl2 solutions. Although the exact stoichiometry of the complex may need to be revisited, this new quaternary complex has a pronounced impact on plutonium predominance diagrams over a broad range of pH, pe, and calcium concentrations that are relevant to nuclear waste disposal.

Comparative analysis of uranium bioassociation with halophilic bacteria and archaea.

Rock salt represents a potential host rock formation for the final disposal of radioactive waste. The interactions between indigenous microorganisms and radionuclides, e.g. uranium, need to be investigated to better predict the influence of microorganisms on the safety assessment of the repository. Hence, the association process of uranium with two microorganisms isolated from rock salt was comparatively studied. Brachybacterium sp. G1, which was isolated from the German salt dome Gorleben, and Halobacterium noricense DSM15987T, were selected as examples of a moderately halophilic bacterium and an extremely halophilic archaeon, respectively. The microorganisms exhibited completely different association behaviors with uranium. While a pure biosorption process took place with Brachybacterium sp. G1 cells, a multistage association process occurred with the archaeon. In addition to batch experiments, in situ attenuated total reflection Fourier-transform infrared spectroscopy was applied to characterize the U(VI) interaction process. Biosorption was identified as the dominating process for Brachybacterium sp. G1 with this method. Carboxylic functionalities are the dominant interacting groups for the bacterium, whereas phosphoryl groups are also involved in U(VI) association by the archaeon H. noricense.

Multistage bioassociation of uranium onto an extremely halophilic archaeon revealed by a unique combination of spectroscopic and microscopic techniques.

The interactions of two extremely halophilic archaea with uranium were investigated at high ionic strength as a function of time, pH and uranium concentration. Halobacterium noricense DSM-15987 and Halobacterium sp. putatively noricense, isolated from the Waste Isolation Pilot Plant repository, were used for these investigations. The kinetics of U(VI) bioassociation with both strains showed an atypical multistage behavior, meaning that after an initial phase of U(VI) sorption, an unexpected interim period of U(VI) release was observed, followed by a slow reassociation of uranium with the cells. By applying in situ attenuated total reflection Fourier-transform infrared spectroscopy, the involvement of phosphoryl and carboxylate groups in U(VI) complexation during the first biosorption phase was shown. Differences in cell morphology and uranium localization become visible at different stages of the bioassociation process, as shown with scanning electron microscopy in combination with energy dispersive X-ray spectroscopy. Our results demonstrate for the first time that association of uranium with the extremely halophilic archaeon is a multistage process, beginning with sorption and followed by another process, probably biomineralization.

Surface complexation of Neptunium(V) onto whole cells and cell components of Shewanella alga: modeling and experimental study.

We systematically quantified surface complexation of Np(V) onto whole cells, cell wall, and extracellular polymeric substances (EPS) of Shewanella alga strain BrY. We first performed acid and base titrations and used the mathematical model FITEQL to estimate the concentrations and deprotonation constants of specific surface functional groups. Deprotonation constants most likely corresponded to a carboxyl group not associated with amino acids (pK(a) approximately 5), a phosphoryl site (pK(a) approximately 7.2), and an amine site (pK(a) > 10). We then carried out batch sorption experiments with Np(V) and each of the S. alga components as a function of pH. Since significant Np(V) sorption was observed on S. alga whole cells and its components in the pH range 2-5, we assumed the existence of a fourth site: a low-pK(a) carboxyl site (pK(a) approximately 2.4) that is associated with amino acids. We used the SPECIATE submodel of the biogeochemical model CCBATCH to compute the stability constants for Np(V) complexation to each surface functional group. The stability constants were similar for each functional group on S. alga bacterial whole cells, cell walls, and EPS, and they explain the complicated sorption patterns when they are combined with the aqueous-phase speciation of Np(V). For pH < 8, the aquo NpO(2)(+) species was the dominant form of Np(V), and its log K values for the low-pK(a) carboxyl, mid-pK(a) carboxyl, and phosphoryl groups were 1.8, 1.8, and 2.5-3.1, respectively. For pH greater than 8, the key surface ligand was amine >XNH(3)(+), which complexed with NpO(2)(CO(3))(3)(5-). The log K for NpO(2)(CO(3))(3)(5-) complexed onto the amine groups was 3.1-3.9. All of the log K values are similar to those of Np(V) complexes with aqueous carboxyl and N-containing carboxyl ligands. These results help quantify the role of surface complexation in defining actinide-microbiological interactions in the subsurface.

Reduction of Np(V) and precipitation of Np(IV) by an anaerobic microbial consortium.

A combination of experimental, analytical, and modeling investigations shows that an anaerobic, sulfate-reducing consortium reduced Np(V) to Np(IV), with subsequent precipitation of a Np(IV) solid. Precipitation of Np(IV) during growth on pyruvate occurred before sulfate reduction began. H2 stimulated precipitation of Np(IV) when added alone to growing cells, but it slowed precipitation when added along with pyruvate. Increasing concentrations of pyruvate also retarded precipitation. Accumulation of an intermediate pyruvate-fermentation product--probably succinate--played a key role in retarding Np(IV) precipitation by complexing the Np(IV). Hydrogen appears to have two roles in controlling Np precipitation: donating electrons for Np(V) reduction and modulating intermediate levels. That Np(V) is microbially reduced and subsequently precipitated under anaerobic conditions has likely beneficial implications for the containment of Np on lands contaminated by radionuclides, but complexation by fermentation intermediates can prevent immobilization by precipitation.

Mathematical modeling of precipitation and dissolution reactions in microbiological systems.

We expand the biogeochemical model CCBATCH to include a precipitation/dissolution sub-model that contains kinetic and equilibrium options. This advancement extends CCBATCH's usefulness to situations in which microbial reactions cause or are affected by formation or dissolution of a solid phase. The kinetic option employs a rate expression that explicitly includes the intrinsic kinetics for reaction or mass-transport control, the difference from thermodynamic equilibrium, and the aqueous concentration of the rate-limiting metal or ligand. The equilibrium feature can be used alone, and it also serves as check that the kinetic rate never is too fast and "overshoots" equilibrium. The features of the expanded CCBATCH are illustrated by an example in which the precipitation of Fe(OH)3(s) allows the biodegradation of citric acid, even though complexes are strong and not bioavailable. Precipitation releases citrate ligand, and biodegradation of the citrate increases the pH.