Brian A. Powell

Stabilization of Plutonium Nano-Colloids by Epitaxial Distortion on Mineral Surfaces

The subsurface migration of Pu may be enhanced by the presence of colloidal forms of Pu. Therefore, complete evaluation of the risk posed by subsurface Pu contamination needs to include a detailed physical/chemical understanding of Pu colloid formation and interactions of Pu colloids with environmentally relevant solid phases. Transmission electron microscopy (TEM) was used to characterize Pu nanocolloids and interactions of Pu nanocolloids with goethite and quartz. We report that intrinsic Pu nanocolloids generated in the absence of goethite or quartz were 2-5 nm in diameter, and both electron diffraction analysis and HRTEM confirm the expected Fm3m space group with the fcc, PuO2 structure. Plutonium nanocolloids formed on goethite have undergone a lattice distortion relative to the ideal fluorite-type structure, fcc, PuO2, resulting in the formation of a bcc, Pu4O7 structure. This structural distortion results from an epitaxial growth of the plutonium colloid on goethite, leading to stronger binding of plutonium to goethite compared with other minerals such as quartz, where the distortion was not observed. This finding provides new insight for understanding how molecular-scale behavior at the mineral-water interface may facilitate transport of plutonium at the field scale.

Adaptive Interactions between Zinc Oxide Nanoparticles and Chlorella sp

The effects of ZnO nanoparticles (NPs) interacting with single-celled green algae, Chlorella sp., have been found to be bilateral. Specifically, our electron microscopy, plant cell, and fluorescence assays showed that the adsorption and aggregation of ZnO NPs compromised algal cell morphology, viability, and membrane integrity, resulting from zinc ion dissolution as well as possible mechanical cell damage induced by the NPs. Conversely, algal cells displayed a remarkable capability of self-protection by minimizing their surface area through aggregation mediated by the oppositely charged metal ions and suppressing zinc ion release from the NPs through exudation, as evidenced by inductively coupled plasma mass spectrometry, zeta potential, and attenuated total reflectance-Fourier transform infrared spectroscopy. This study illustrates the adaptive nature and complexity in potential ecological response to discharged nanomaterials.

Evaluation of a Radioiodine Plume Increasing in Concentration at the Savannah River Site

Field and laboratory studies were carried out to understand the cause for steady increases in (129)I concentrations emanating from radiological basins located on the Savannah River Site, South Carolina. The basins were closed in 1988 by adding limestone and slag and then capping with a low permeability engineered cover. Groundwater (129)I concentrations in a well near the basins in 1993 were 200 pCi L(-1) and are presently between 400 and 1000 pCi L(-1). Iodine speciation in the plume contained wide ranges of iodide, iodate, and organo-iodine concentrations. First-order calculations based on a basin sediment desorption study indicate that the modest increase of 0.7 pH units detected in the study site groundwater over the last 17 years since closure of the basins may be sufficient to produce the observed increased groundwater (129)I concentrations near the basins. Groundwater monitoring of the plume at the basins has shown that the migration of many of the high risk radionuclides originally present at this complex site has been attenuated. However, (129)I continues to leave the source at a rate that may have been exacerbated by the initial remediation efforts. This study underscores the importance of identifying the appropriate in situ stabilization technologies for all source contaminants, especially if their geochemical behaviors differ.

Np(V) and Pu(V) Ion Exchange and Surface-Mediated Reduction Mechanisms on Montmorillonite

Due to their ubiquity and chemical reactivity, aluminosilicate clays play an important role in actinide retardation and colloid-facilitated transport in the environment. In this work, Pu(V) and Np(V) sorption to Na-montmorillonite was examined as a function of ionic strength, pH, and time. Np(V) sorption equilibrium was reached within 2 h. Sorption was relatively weak and showed a pH and ionic strength dependence. An approximate NpO(2)(+) → Na(+) Vanselow ion exchange coefficient (Kv) was determined on the basis of Np(V) sorption in 0.01 and 1.0 M NaCl solutions at pH < 5 (Kv ~ 0.3). In contrast to Np(V), Pu(V) sorption equilibrium was not achieved on the time-scale of weeks. Pu(V) sorption was much stronger than Np(V), and sorption rates exhibited both a pH and ionic strength dependence. Differences in Np(V) and Pu(V) sorption behavior are indicative of surface-mediated transformation of Pu(V) to Pu(IV) which has been reported for a number of redox-active and redox-inactive minerals. A model of the pH and ionic strength dependence of Pu(V) sorption rates suggests that H(+) exchangeable cations facilitate Pu(V) reduction. While surface complexation may play a dominant role in Pu sorption and colloid-facilitated transport under alkaline conditions, results from this study suggest that Pu(V) ion exchange and surface-mediated reduction to Pu(IV) can immobilize Pu or enhance its colloid-facilitated transport in the environment at neutral to mildly acidic pHs.

Surface Complexation Modeling of Eu(III) and U(VI) Interactions with Graphene Oxide

Graphene oxide (GO) has great potential for actinide removal due to its extremely high sorption capacity, but the mechanism of sorption remains unclear. In this study, the carboxylic functional group and an unexpected sulfonate functional group on GO were characterized as the reactive surface sites and quantified via diffuse layer modeling of the GO acid/base titrations. The presence of sulfonate functional group on GO was confirmed using elemental analysis and X-ray photoelectron spectroscopy. Batch experiments of Eu(III) and U(VI) sorption to GO as the function of pH (1-8) and as the function of analyte concentration (10-100, 000 ppb) at a constant pH ≈ 5 were conducted; the batch sorption results were modeled simultaneously using surface complexation modeling (SCM). The SCM indicated that Eu(III) and U(VI) complexation to carboxylate functional group is the main mechanism for their sorption to GO; their complexation to the sulfonate site occurred at the lower pH range and the complexation of Eu(III) to sulfonate site are more significant than that of U(VI). Eu(III) and U(VI) facilitated GO aggregation was observed with high Eu(III) and U(VI) concentration and may be caused by surface charge neutralization of GO after sorption.

Quantitative Measurement of Ligand Exchange on Iron Oxides via Radiolabeled Oleic Acid

Ligand exchange of hydrophilic molecules on the surface of hydrophobic iron oxide nanoparticles produced via thermal decomposition of chelated iron precursors is a common method for producing aqueous suspensions of particles for biomedical applications. Despite the wide use, relatively little is understood about the efficiency of ligand exchange on the surface of iron oxide nanoparticles and how much of the hydrophobic ligand is removed. To address this issue, we utilized a radiotracer technique to track the exchange of a radiolabeled (14)C-oleic acid ligand with hydrophilic ligands on the surface of magnetite nanoparticles. Iron oxide nanoparticles functionalized with (14)C-oleic acid were modified with poly(ethylene glycol) with terminal functional groups including, L-3,4-dihydroxyphenylalanine, a nitrated L-3,4-dihydroxyphenylalanine, carboxylic acid, a phosphonate, and an amine. Following ligand exchange, the nanoparticles and byproducts were analyzed using liquid scintillation counting and inductively coupled plasma mass spectroscopy. The labeled and unlabeled particles were further characterized by transmission electron microscopy and dynamic light scattering to determine particle size, hydrodynamic diameter, and zeta potential. The unlabeled particles were characterized via thermogravimetric analysis and vibrating sample magnetometry. Radioanalytical determination of the (14)C from (14)C-oleic acid was used to calculate the amount of oleic acid remaining on the surface of the particles after purification and ligand exchange. There was a significant loss of oleic acid on the surface of the particles after ligand exchange with amounts varying for the different functional binding groups on the poly(ethylene glycol). Nonetheless, all samples demonstrated some residual oleic acid associated with the particles. Quantification of the oleic acid remaining after ligand exchange reveals a binding hierarchy in which catechol derived anchor groups displace oleic acid on the surface of the nanoparticles better than the phosphonate, followed by the amine and carboxylic acid groups. Furthermore, the results show that these ligand exchange reactions do not necessarily occur to completion as is often assumed, thus leaving a residual amount of oleic acid on the surface of the particles. A thorough analysis of ligand exchange is required to develop nanoparticles that are suitable for their desired application.

Pu(V) and Pu(IV) Sorption to Montmorillonite

Plutonium (Pu) adsorption to and desorption from mineral phases plays a key role in controlling the environmental mobility of Pu. Here we assess whether the adsorption behavior of Pu at concentrations used in typical laboratory studies (≥10(-10) [Pu] ≤ 10(-6) M) are representative of adsorption behavior at concentrations measured in natural subsurface waters (generally <10(-12) M). Pu(V) sorption to Na-montmorillonite was examined over a wide range of initial Pu concentrations (10(-6)-10(-16) M). Pu(V) adsorption after 30 days was linear over the wide range of concentrations studied, indicating that Pu sorption behavior from laboratory studies at higher concentrations can be extrapolated to sorption behavior at low, environmentally relevant concentrations. Pu(IV) sorption to montmorillonite was studied at initial concentrations of 10(-6)-10(-11) M and was much faster than Pu(V) sorption over the 30 day equilibration period. However, after one year of equilibration, the extent of Pu(V) adsorption was similar to that observed for Pu(IV) after 30 days. The continued uptake of Pu(V) is attributed to a slow, surface-mediated reduction of Pu(V) to Pu(IV). Comparison between rates of adsorption of Pu(V) to montmorillonite and a range of other minerals (hematite, goethite, magnetite, groutite, corundum, diaspore, and quartz) found that minerals containing significant Fe and Mn (hematite, goethite, magnetite, and groutite) adsorbed Pu(V) faster than those which did not, highlighting the potential importance of minerals with redox couples in increasing the rate of Pu(V) removal from solution.

Influence of iron redox transformations on plutonium sorption to sediments

Abstract Plutonium subsurface mobility is primarily controlled by its oxidation state, which in turn is loosely coupled to the oxidation state of iron in the system. Experiments were conducted to examine the effect of sediment iron mineral composition and oxidation state on plutonium sorption and reduction. A pH 6.3 vadose zone sediment containing iron oxides and iron-containing phyllosilicates was treated with various complexants (ammonium oxalate) and reductants (hydroxylamine hydrochloride and dithionite-citrate-bicarbonate (DCB)) to selectively leach and/or reduce iron oxide and phyllosilicate/clay Fe(III). 57Fe-Mössbauer spectroscopy was used to identify initial iron mineral composition of the sediment and monitor dissolution and reduction of iron oxides and reduction of phyllosilicate Fe(III). 57Fe-Mössbauer spectroscopy showed that the Fe-mineral composition of the untreated sediment is: 25–30% hematite, 60–65% small-particle/Al-goethite, and <10% Fe(III) in phyllosilicate; there was no detectable Fe(II). Upon reduction with a strong chemical reductant (dithionite-citrate-bicarbonate buffer), much of the hematite and goethite was removed. Partial reduction of phyllosilicate Fe(III) was evident in the sediments subjected to DCB treatment. Sorption of Pu(V) was monitored over one week for the untreated and each of five treated sediment fractions. Plutonium oxidation state speciation in the aqueous and solid phases was monitored using solvent extraction, coprecipitation, and XANES. The rate of sorption appears to correlate with the fraction of Fe(II) in the sediment (untreated or treated). Pu(V) was the only oxidation state measured in the aqueous phase, irrespective of treatment, whereas Pu(IV) and much smaller amounts of Pu(V) and Pu(VI) were measured in the solid phase. Surface-mediated reduction of Pu(V) to Pu(IV) occurred in treated and untreated sediment samples; Pu(V) remained on untreated sediment surface for two days before reducing to Pu(IV). Similar to the sorption kinetics, the reduction rate appears to be correlated with sediment Fe(II) concentration. The correlation between Fe(II) concentrations and Pu(V) reduction demonstrates the potential impact of changing iron mineralogy on plutonium subsurface transport through redox transition areas. These findings should influence the conceptual models of long-term stewardship of Pu contaminated sites that have fluctuating redox conditions, such as vadose zones or riparian zones.

Examination of the effect of alpha radiolysis on plutonium(V) sorption to quartz using multiple plutonium isotopes

The objective of this research was to determine if radiolysis at the mineral surface was a plausible mechanism for surface-mediated reduction of plutonium. Batch sorption experiments were used to monitor the amount of plutonium sorbed to high-purity quartz as a function of time, pH, and total alpha radioactivity. Three systems were prepared using both (238)Pu and (242)Pu in order to increase the total alpha radioactivity of the mineral suspensions while maintaining a constant plutonium concentration. The fraction of sorbed plutonium increased with increasing time and pH regardless of the total alpha radioactivity of the system. Increasing the total alpha radioactivity of the solution had a negligible effect on the sorption rate. This indicated that surface-mediated reduction of Pu(V) in these systems was not due to radiolysis. Additionally, literature values for the Pu(V) disproportionation rate constant did not describe the experimental results. Therefore, Pu(V) disproportionation was also not a main driver for surface-mediated reduction of plutonium. Batch desorption experiments and X-ray absorption near edge structure spectroscopy were used to show that Pu(IV) was the dominant oxidation state of sorbed plutonium. Thus, it appears that the observed surface-mediated reduction of Pu(V) in the presence of high-purity quartz was based on the thermodynamic favorability of a Pu(IV) surface complex.

Effect of Fulvic Acid Surface Coatings on Plutonium Sorption and Desorption Kinetics on Goethite

The rates and extent of plutonium (Pu) sorption and desorption onto mineral surfaces are important parameters for predicting Pu mobility in subsurface environments. The presence of natural organic matter, such as fulvic acid (FA), may influence these parameters. We investigated the effects of FA on Pu(IV) sorption/desorption onto goethite in two scenarios: when FA was (1) initially present in solution or (2) found as organic coatings on the mineral surface. A low pH was used to maximize FA coatings on goethite. Experiments were combined with kinetic modeling and speciation calculations to interpret variations in Pu sorption rates in the presence of FA. Our results indicate that FA can change the rates and extent of Pu sorption onto goethite at pH 4. Differences in the kinetics of Pu sorption were observed as a function of the concentration and initial form of FA. The fraction of desorbed Pu decreased in the presence of FA, indicating that organic matter can stabilize sorbed Pu on goethite. These results suggest that ternary Pu-FA-mineral complexes could enhance colloid-facilitated Pu transport. However, more representative natural conditions need to be investigated to quantify the relevance of these findings.