In order to accurately model and predict the fate and transport of metals and radionuclides at multiple radio-contaminated sites, there is a need for an understanding on how metals such as technetium interact with their environment. Many contaminated sites are known to contain large amounts of organic ligands that can affect the solubility and mobility of metals. This study focuses on the effect of acetate on the complexation and dissolution of Tc(IV). Studies were performed at pcH 4.5 (±0.3), at which TcOOH + is the predominant species. The stability constants for the TcOOHacetate complex were determined at ionic strengths varying from 0.5 to 3.0 M (NaCl), using a solvent extraction method. The stability constants showed the expected increasing trend over the range of ionic strengths, from 2.46 ± 0.03 (I = 0.5) to 3.09 ± 0.08 (I = 3.0). A stability constant of 2.8 ± 0.16 at zero ionic strength was determined by specific ion interaction theory. Geochemical modeling data suggest that the dissolution of TcO 2 ·1.6H 2 O is not greatly affected by the presence of acetate, at concentrations equal or less than 20 mM.

Degradation rates of benzene, p-xylene, naphthalene, and o-dichlorobenzene have been measured in a heterogeneous, unconfined aquifer during a pulse injection experiment at Columbus Air ForceBase, Columbus, Mississippi. Dissolved oxygen in the pulse plume maintained aerobic conditions. Degradation kinetics calculated from the complete field data set were approximately first order with the following rate constants: benzene, 0.0070 d-l; p-xylene, 0.0107 d -•; naphthalene, 0.0064 d -l; and o-dichlorobenzene, 0.0046 d-1. Reaction rates were also calculated from a near-field subset of the data using a model based on the hydrologic characteristics of the aquifer. Shapes of the degradation rate curves were consistent with microbial degradation processes. Maximum degradation rates obtained are presumed to be characteristic of the microbial population metabolism. Carbon 14-1abeled p-xylene was included in the injection solution to permit detection of degradation products. This technique is suggested for future field experiments, because it distinguishes solute degradation from solute losses by sorption and evaporation and allows mass balance to be demonstrated throughout the course of the reaction in the aquifer.

To understand the key processes affecting 99Tc mobility in the subsurface and help with the remediation of contaminated sites, the binding constants of several humic substances (humic and fulvic acids) with Tc(IV) were determined, using a solvent extraction technique. The novelty of this paper lies in the determination of the binding constants of the complexes formed with the individual species TcO(OH)+ and TcO(OH)2(0). Binding constants were found to be 6.8 and between 3.9 and 4.3, for logβ1,-1,1 and logβ1,-2,1, respectively; these values were little modified by a change of ionic strength, in most cases, between 0.1 and 1.0 M, nor were they by the nature and origin of the humic substances. Modeling calculations based on these show TcO(OH)-HA to be the predominant complex in a system containing 20 ppm HA and in the 4-6 pH range, whereas TcO(OH)2(0) and TcO(OH)2-HA are the major species, in the pH 6-8 range.

Safe and effective nuclear waste disposal, as well as accidental radionuclide releases, necessitates our understanding of the fate of radionuclides in the environment, including their interaction with microorganisms. We examined the sorption of Pu(IV) and Pu(V) to Pseudomonas sp. strain EPS-1W, an aerobic bacterium isolated from plutonium (Pu)-contaminated groundwater collected in the United States at the Nevada National Security Site (NNSS) in Nevada. We compared Pu sorption to cells with and without bound extracellular polymeric substances (EPS). Wild-type cells with intact EPS sorbed Pu(V) more effectively than cells with EPS removed. In contrast, cells with and without EPS showed the same sorption affinity for Pu(IV). In vitro experiments with extracted EPS revealed rapid reduction of Pu(V) to Pu(IV). Transmission electron microscopy indicated that 2-to 3-nm nanocrystalline Pu(IV)O 2 formed on cells equilibrated with high concentrations of Pu(IV) but not Pu(V). Thus, EPS, while facilitating Pu(V) reduction, inhibit the formation of nanocrystalline Pu(IV) precipitates. IMPORTANCEOur results indicate that EPS are an effective reductant for Pu(V) and sorbent for Pu(IV) and may impact Pu redox cycling and mobility in the environment. Additionally, the resulting Pu morphology associated with EPS will depend on the concentration and initial Pu oxidation state. While our results are not directly applicable to the Pu transport situation at the NNSS, the results suggest that, in general, stationary microorganisms and biofilms will tend to limit the migration of Pu and provide an important Pu retardation mechanism in the environment. In a broader sense, our results, along with a growing body of literature, highlight the important role of microorganisms as producers of redox-active organic ligands and therefore as modulators of radionuclide redox transformations and complexation in the subsurface.T he civil production of nuclear energy and military production of nuclear materials have resulted in an estimated worldwide inventory of over 2,000 metric tons of plutonium (Pu) (1). This inventory continues to increase at a rate of approximately 70 metric tons per year as a result of global nuclear energy production (2). Due to its long half-life (24,100 years for 239 Pu) and high radiotoxicity (3), Pu is an important driver in public health risk assessments for nuclear waste repositories and radiologically contaminated sites. However, predicting how Pu behaves in the environment and ultimately calculating its human health risk are limited by our understanding of the dominant biogeochemical processes controlling its behavior.The behavior of Pu in the environment is strongly dependent on its oxidation state and concentration. Among all the actinides, Pu has one of the most complex chemical, redox, and surface sorption behaviors. At low concentrations, Pu can exist as aqueous species in the III, IV, V, and/or VI oxidation states, all of which have different solubilities (4), mineral sorption affinities (5-7), and hence...

The stability constant for Tc(IV)/EDTA complexes were determined using a solvent extraction technique at varying ionic strength (NaCl) and the specific ion interaction theory model allowed for calculating stability constants at zero ionic strength. The stability constants at zero ionic strength for the formation of the TcOEDTA2− and TcOHEDTA− complexes are 1020.0 ± 0.4 and 1025.3 ± 0.5, respectively. The modeled Tc(IV) solubility was calculated to be 3.9 × 10−7 M at near-neutral pH and in presence of 2.5 mM EDTA, a result found to be in good agreement with published solubility experimental data. Speciation calculations showed that TcOEDTA2− is the predominant species between pH 4 and 7.5 in presence of 0.171 mM EDTA, while TcO(OH)2 0 is predominant in basic solution. These studies show that EDTA has a very strong affinity for complexation with Tc(IV) and can increase the environmental mobility of Tc(IV).

Approximately 2.8 t of plutonium (Pu) has been deposited in the Nevada National Security Site (NNSS) subsurface as a result of underground nuclear testing. Most of this Pu is sequestered in nuclear melt glass. However, Pu migration has been observed and attributed to colloid facilitated transport. To identify the mechanisms controlling Pu mobilization, longterm (∼3 year) laboratory nuclear melt glass alteration experiments were performed at 25 to 200 °C to mimic hydrothermal conditions in the vicinity of underground nuclear tests. The clay and zeolite colloids produced in these experiments are similar to those identified in NNSS groundwater. At 200 °C, maximum Pu and colloid concentrations of 30 Bq/L and 150 mg/L, respectively, were observed. However, much lower Pu and colloid concentrations were observed at 25 and 80 °C. These data suggest that Pu concentrations above the drinking water Maximum Contaminant Levels (0.56 Bq/L) may exist during early hydrothermal conditions in the vicinity of underground nuclear tests. However, formation of colloid-associated Pu will tend to decrease with time as nuclear test cavity temperatures decrease. Furthermore, median colloid concentrations in NNSS groundwater (1.8 mg/ L) suggest that the high colloid and Pu concentrations observed in our 140 and 200 °C experiments are unlikely to persist in downgradient NNSS groundwater. While our experiments did not span all groundwater and nuclear melt glass conditions that may be present at the NNSS, our results are consistent with the documented low Pu concentrations in NNSS groundwater.

Two aqueous PuIV‐desferrioxamine B (DFOB) complexes were characterized by one‐ and two‐dimensional NMR techniques and an unexpected dimeric PuIVDFOB‐di‐μ‐(O/OH)‐PuIVDFOB complex was identified. Both “Curie” and “anti‐Curie” behavior were observed for the dimeric species, yet the monomeric species only showed “anti‐Curie” behavior. Diffusion ordered spectroscopy experiments showed an increase in particle size for the two species, which is indicative of a dimeric species. Bond lengths and coordination numbers estimated from X‐ray absorption spectroscopy are consistent with the proposed structures.

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