Dien Li

Sorption coefficients and molecular mechanisms of Pu, U, Np, Am and Tc to Fe (hydr)oxides: a review.

Pu, U, Np, Am and Tc are among the major risk drivers at nuclear waste management facilities throughout the world. Furthermore, uranium mining and milling operations have generated an enormous legacy of radioactively contaminated soils and groundwater. The sorption process of radionulcides onto ubiquitous Fe (hydr)oxides (FHOs; hematite, magnetite, goethite and ferrihydrite) is one of the most vital geochemical processes controlling the transport and fate of radionuclides and nuclear wastes in the subsurface zones. Meanwhile, understanding molecular-level chemical speciation of radionuclides onto FHOs is crucial to model their behavior in subsurface environments, and to develop new technologies for nuclear waste treatment and long-term remediation strategies for contaminated soils and groundwater. This review article aims (1) to provide risk or performance assessment modelers with macroscopic distribution coefficient (K(d)) data of Pu, U, Np, Am and Tc onto FHOs under different conditions (pH, radionuclide concentration, solution ion strength, sorbent loading, partial pressure of CO(2) (P CO(2)), equilibrium time) pertinent to environmental and engineered systems, and (2) to provide a microscopic or molecular-level understanding of the chemical speciation and sorption processes of these radionuclides to FHOs.

Uranium immobilization in an iron-rich rhizosphere of a native wetland plant from the Savannah River Site under reducing conditions.

The hypothesis of this study was that iron plaques formed on the roots of wetland plants and their rhizospheres create environmental conditions favorable for iron reducing bacteria that promote the in situ immobilization of uranium. Greenhouse microcosm studies were conducted using native plants (Sparganium americanum) from a wetland located on the Savannah River Site, Aiken, SC. After iron plaques were established during a 73-day period by using an anoxic Fe(II)-rich nutrient solution, a U(VI) amended nutrient solution was added to the system for an additional two months. Compared to plant-free control microcosms, microcosms containing iron plaques successfully stimulated the growth of targeted iron reducing bacteria, Geobacter spp. Their population continuously increased after the introduction of the U(VI) nutrient solution. The reduction of some of the U(VI) to U(IV) by iron reducing bacteria was deduced based on the observations that the aqueous Fe(II) concentrations increased while the U(VI) concentrations decreased. The Fe(II) produced by the iron reducing bacteria was assumed to be reoxidized by the oxygen released from the roots. Advanced spectroscopic analyses revealed that a significant fraction of the U(VI) had been reduced to U(IV) and they were commonly deposited in association with phosphorus on the iron plaque.

Functionalized magnetic mesoporous silica nanoparticles for U removal from low and high pH groundwater

U(VI) species display limited adsorption onto sediment minerals and synthetic sorbents in pH <4 or pH >8 groundwater. In this work, magnetic mesoporous silica nanoparticles (MMSNs) with magnetite nanoparticle cores were functionalized with various organic molecules using post-synthetic methods. The functionalized MMSNs were characterized using N2 adsorption-desorption isotherms, thermogravimetric analysis (TGA), transmission electron microscopy (TEM), (13)C cross polarization and magic angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectroscopy, and powder X-ray diffraction (XRD), which indicated that mesoporous silica (MCM-41) particles of 100-200nm formed around a core of magnetic iron oxide, and the functional groups were primarily grafted into the mesopores of ∼3.0nm in size. The functionalized MMSNs were effective for U removal from pH 3.5 and 9.6 artificial groundwater (AGW). Functionalized MMSNs removed U from the pH 3.5 AGW by as much as 6 orders of magnitude more than unfunctionalized nanoparticles or silica and had adsorption capacities as high as 38mg/g. They removed U from the pH 9.6 AGW as much as 4 orders of magnitude greater than silica and 2 orders of magnitude greater than the unfunctionalized nanoparticles with adsorption capacities as high as 133mg/g. These results provide an applied solution for treating U contamination that occurs at extreme pH environments and a scientific foundation for solving critical industrial issues related to environmental stewardship and nuclear power production.

Spectroscopic Evidence of Uranium Immobilization in Acidic Wetlands by Natural Organic Matter and Plant Roots

Biogeochemistry of uranium in wetlands plays important roles in U immobilization in storage ponds of U mining and processing facilities but has not been well understood. The objective of this work was to study molecular mechanisms responsible for high U retention by Savannah River Site (SRS) wetland sediments under varying redox and acidic (pH = 2.6-5.8) conditions using U L3-edge X-ray absorption spectroscopy. Uranium in the SRS wetland sediments existed primarily as U(VI) bonded as a bidentate to carboxylic sites (U-C bond distance at ∼2.88 Å), rather than phenolic or other sites of natural organic matter (NOM). In microcosms simulating the SRS wetland processes, U immobilization on roots was 2 orders of magnitude higher than on the adjacent brown or more distant white sands in which U was U(VI). Uranium on the roots were both U(IV) and U(VI), which were bonded as a bidentate to carbon, but the U(VI) may also form a U phosphate mineral. After 140 days of air exposure, all U(IV) was reoxidized to U(VI) but remained as a bidentate bonding to carbon. This study demonstrated NOM and plant roots can highly immobilize U(VI) in the SRS acidic sediments, which has significant implication for the long-term stewardship of U-contaminated wetlands.

Mobile colloid generation induced by a cementitious plume: mineral surface-charge controls on mobilization.

Cementitious materials are increasingly used as engineered barriers and waste forms for radiological waste disposal. Yet their potential effect on mobile colloid generation is not well-known, especially as it may influence colloid-facilitated contaminant transport. Whereas previous papers have studied the introduction of cement colloids into sediments, this study examined the influence of cement leachate chemistry on the mobilization of colloids from a subsurface sediment collected from the Savannah River Site, USA. A sharp mobile colloid plume formed with the introduction of a cement leachate simulant. Colloid concentrations decreased to background concentrations even though the aqueous chemical conditions (pH and ionic strength) remained unchanged. Mobile colloids were mainly goethite and to a lesser extent kaolinite. The released colloids had negative surface charges and the mean particle sizes ranged primarily from 200 to 470 nm. Inherent mineralogical electrostatic forces appeared to be the controlling colloid removal mechanism in this system. In the background pH of ~6.0, goethite had a positive surface charge, whereas quartz (the dominant mineral in the immobile sediment) and kaolinite had negative surface charges. Goethite acted as a cementing agent, holding kaolinite and itself onto the quartz surfaces due to the electrostatic attraction. Once the pH of the system was elevated, as in the cementitious high pH plume front, the goethite reversed to a negative charge, along with quartz and kaolinite, then goethite and kaolinite colloids were mobilized and a sharp spike in turbidity was observed. Simulating conditions away from the cementitious source, essentially no colloids were mobilized at 1:1000 dilution of the cement leachate or when the leachate pH was ≤ 8. Extreme alkaline pH environments of cementitious leachate may change mineral surface charges, temporarily promoting the formation of mobile colloids.

Iron mineralogy and uranium-binding environment in the rhizosphere of a wetland soil

Wetlands mitigate the migration of groundwater contaminants through a series of biogeochemical gradients that enhance multiple contaminant-binding processes. The hypothesis of this study was that wetland plant roots contribute organic carbon and release O2 within the rhizosphere (plant-impact soil zone) that promote the formation of Fe(III)-(oxyhydr)oxides. In turn, these Fe(III)-(oxyhydr)oxides stabilize organic matter that together contribute to contaminant immobilization. Mineralogy and U binding environments of the rhizosphere were evaluated in samples collected from contaminated and non-contaminated areas of a wetland on the Savannah River Site in South Carolina. Based on Mössbauer spectroscopy, rhizosphere soil was greatly enriched with nanogoethite, ferrihydrite-like nanoparticulates, and hematite, with negligible Fe(II) present. X-ray computed tomography and various microscopy techniques showed that root plaques were tens-of-microns thick and consisted of highly oriented Fe-nanoparticles, suggesting that the roots were involved in creating the biogeochemical conditions conducive to the nanoparticle formation. XAS showed that a majority of the U in the bulk wetland soil was in the +6 oxidation state and was not well correlated spatially to Fe concentrations. SEM/EDS confirm that U was enriched on root plaques, where it was always found in association with P. Together these findings support our hypothesis and suggest that plants can alter mineralogical conditions that may be conducive to contaminant immobilization in wetlands.

Removal capacity and chemical speciation of groundwater iodide (I−) and iodate (IO3−) sequestered by organoclays and granular activated carbon

Radioiodine (present mostly as 129I) is difficult to remove from waste streams or contaminated groundwater because it tends to exist as multiple anionic species (i.e., iodide (I-), iodate (IO3-) and organo-iodide) that do not bind to minerals or synthetic materials. In this work, the efficacy of organoclay OCB and OCM, and granular activated carbon (GAC) as sorbents to bind I- and IO3- from artificial groundwater (AGW) was examined. These sorbents were highly effective at removing I- and IO3- from AGW under oxic condition, with the adsorption capacity up to 30 mg I/g sorbent. Based on X-ray spectroscopy measurements, I- was bound to organic ligands in organoclays OCB and OCM, but when GAC was exposed to I- in groundwater, the sequestered I species was molecular I2. For IO3- interacting with organoclay OCB and GAC, the adsorbed I species remained being IO3-, but when organoclay OCM that contains both quaternary amine and sulfur was exposed to IO3-, the sulfur compound would reduce IO3- to I- that was then bound to organic ligands. Thus, the inexpensive and high-capacity organoclays and GAC may provide a practical solution for removing 129I contaminant from environmental systems and liquid nuclear wastes.