Ionic strength and composition affect the mobility of surface-modified Fe0 nanoparticles in water-saturated sand columns

The surfaces of nanoscale zerovalent iron (NZVI) used for groundwater remediation must be modified to be mobile in the subsurface for emplacement. Adsorbed polymers and surfactants can electrostatically, sterically, or electrosterically stabilize nanoparticle suspensions in water, but their efficacy will depend on groundwater ionic strength and cation type as well as physical and chemical heterogeneities of the aquifer material. Here, the effect of ionic strength and cation type on the mobility of bare, polymer-, and surfactant-modified NZVI is evaluated in water-saturated sand columns at low particle concentrations where filtration theory is applicable. NZVI surface modifiers include a high molecular weight (MW) (125 kg/mol) poly(methacrylic acid)-b-(methyl methacrylate)-b-(styrene sulfonate) triblock copolymer (PMAA-PMMA-PSS), polyaspartate which is a low MW (2-3 kg/mol) biopolymer, and the surfactant sodium dodecyl benzene sulfonate (SDBS, MW = 348.5 g/mol). Bare NZVI with an apparent zeta-potential of -30 +/- 3 mV was immobile. Polyaspartate-modified nanoiron (MRNIP) with an apparent zeta-potential of -39 +/- 1 mV was mobile at low ionic strengths (< 40 mM for Na+ and < 0.5 mM for Ca2+), and had a critical deposition concentration (CDC) of approximately 770 mM Na+ and approximately 4 mM for Ca2+. SDBS-modified NZVI with a similar apparent zeta-potential (-38.3 +/- 0.9 mV) showed similar behavior (CDC approximately 350 mM for Na+ and approximately 3.5 mM for Ca2+). Triblock copolymer-modified NZVI had the highest apparent zeta-potential (-50 +/- 1.2 mV), the greatest mobility in porous media, and a CDC of approximately 4 M for Na+ and approximately 100s of mM for Ca2+. The high mobility and CDC is attributed to the electrosteric stabilization afforded by the triblock copolymer but not the other modifiers which provide primarily electrostatic stabilization. Thus, electrosteric stabilization provides the best resistance to changing electrolyte conditions likely to be encountered in real groundwater aquifers, and may provide transport distances of 10s to 100s of meters in unconsolidated sandy aquifers at injection velocities used for emplacement.     

Iron nanoparticles coated with amphiphilic polysiloxane graft copolymers: dispersibility and contaminant treatability

Amphiphilic polysiloxane graft copolymers (APGCs) were used as a delivery vehicle for nanoscale zerovalent iron (NZVI). The APGCs were designed to enable adsorption onto NZVI surfaces via carboxylic acid anchoring groups and polyethylene glycol (PEG) grafts were used to provide dispersibility in water. Degradation studies were conducted with trichloroethylene (TCE) as the model contaminant. TCE degradation rate with APGC-coated NZVI (CNZVI) was determined to be higher as compared to bare NZVI. The surface normalized degradation rate constants, k(SA) (Lm(2-) h(-1)), for TCE removal by CNZVI and bare NZVI ranged from 0.008 to 0.0760 to 007-0.016, respectively. Shelf life studies conducted over 12 months to access colloidal stability and 6 months to access TCE degradation indicated that colloidal stability and chemical reactivity of CNZVI remained more or less unchanged. The sedimentation characteristics of CNZVI under different ionic strength conditions (0-10 mM) did not change significantly. The steric nature of particle stabilization is expected to improve aquifer injection efficiency of the coated NZVI for groundwater remediation.     

Engineered polymeric nanoparticles for bioremediation of hydrophobic contaminants

Sorption of hydrophobic organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs), to soil has been shown to limit their solubilization rate and mobility. In addition, sequestration of contaminants by sorption to soil and by partitioning in nonaqueous phase liquids (NAPLs) reduces their bioavailability. Polymeric nano-network particles have been demonstrated to increase the "effective" solubility of a representative hydrophobic organic contaminant, phenanthrene (PHEN) and to enhance the release of PHEN from contaminated aquifer material. In this study, we investigate the usefulness of nanoparticles made from a poly(ethylene) glycol modified urethane acrylate (PMUA) precursor chain, in enhancing the bioavailability of PHEN. PMUA nanoparticles are shown to increase the mineralization rate of PHEN crystal in water, PHEN sorbed on aquifer material, and PHEN dissolved in a model NAPL (hexadecane) in the presence of aquifer media. These results show that PMUA particles not only enhance the release of sorbed and NAPL-sequestered PHEN but also increase its mineralization rate. The accessibility of contaminants in PMUA particles to bacteria also suggests that particle application may be an effective means to enhance the in-situ biodegradation rate in remediation through natural attenuation of contaminants. In pump-and-treat or soil washing remediation schemes, bioreactors could be used to recycle extracted nanoparticles. The properties of PMUA nanoparticles are shown to be stable in the presence of a heterogeneous active bacterial population, enabling them to be reused after PHEN bound to the particles has been degraded by bacteria.     

Apparent decreases in colloid deposition rate coefficients with distance of transport under unfavorable deposition conditions: a general phenomenon

The transport of polystyrene microspheres was examined in packed glass beads under a variety of environmentally relevant ionic strength and flow conditions. The observed profiles of numbers of retained microspheres versus distance from the column entrance were much steeper than expected based on a constant rate coefficient of deposition acrossthe length of the column, indicating apparent decreases in deposition rate coefficients with transport distance. Deviation in the profile from log-linear decreases with distance was greatest under highly unfavorable conditions (low ionic strength), relatively reduced under mildly unfavorable conditions (high ionic strength), and was eliminated under favorable conditions. The generality of apparent decreases in deposition rate coefficients with distance of transport among microspheres, bacteria, and viruses leads to the conclusion that such effects reflect processes that are fundamental to filtration under unfavorable conditions. Numerical simulations of experiments that were performed under unfavorable conditions utilized a log-normal distribution of deposition rate coefficients among the colloid population in orderto simulate the effluent curves and retained profiles simultaneously. It is shown that while straining could be a significant contributor to the steep retained profiles at low ionic strength, where overall retention is low, distribution in interaction potentials among the population was a viable mechanism that can yield apparent decreases in deposition rate coefficients with distance of transport.     

Interactions of Tc(IV) with humic substances

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.     

Hierarchical approach to model multilayer colloidal deposition in porous media

Particle deposition is important in many environmental systems such as water and wastewater filtration, air pollution control, subsurface transport, biofilm formation and fouling, and thin film synthesis for use in remediation technologies. While continuum-level models have been developed to predict deposition dynamics in these systems, these models fail to explain transient dynamics of multilayer deposition from a mechanistic viewpoint. In this work, a multiscale approach has been developed to predict multiple layer irreversible colloidal deposition in the presence of interparticle electrostatic and van der Waals interactions in porous media. The approach combines the kinetic information obtained from the mesoscopic stochastic simulations of particle deposition with the macroscopic conservation equation describing colloidal transport. Sequential Brownian dynamics simulations are first performed by accounting for particle-particle (P-P) and particle-surface (P-S) interactions, and multilayered particle deposits are obtained. The available surface function quantifying the deposition kinetics is then obtained from the deposit microstructure. Deposition dynamics are studied at different ionic strengths and particle potentials that control the range and magnitude of interparticle interactions. Simulation results showed that the microstructure of the particle deposits formed under the influence of P-P and P-S electrostatic interactions exhibited significant variations with respect to ionic strength and could be qualitatively explained bythe interplay between the repulsive and attractive P-P and P-S interaction forces. The available surface function also varied significantly as a function of ionic strength. This basic understanding of the deposition dynamics at the mesoscale was then combined with the continuum-level transport equations to predict particle breakthrough curves in porous media. The approach is capable of capturing transient features of deposition dynamics, as demonstrated by the good agreement between the model predictions and the experimental observations.     

In situ stimulation of groundwater denitrification with formate to remediate nitrate contamination

In situ stimulation of denitrification has been proposed as a mechanism to remediate groundwater nitrate contamination. In this study, sodium formate was added to a sand and gravel aquifer on Cape Cod, MA, to test whether formate could serve as a potential electron donor for subsurface denitrification. During 16- and 10-day trials, groundwater from an anoxic nitrate-containing zone (0.5-1.5 mM) was continuously withdrawn, amended with formate and bromide, and pumped back into the aquifer. Concentrations of groundwater constituents were monitored in multilevel samplers after up to 15 m of transport by natural gradient flow. Nitrate and formate concentrations were decreased 80-100% and 60-70%, respectively, with time and subsequent travel distance, while nitrite concentrations inversely increased. The field experiment breakthrough curves were simulated with a two-dimensional site-specific model that included transport, denitrification, and microbial growth. Initial values for model parameters were obtained from laboratory incubations with aquifer core material and then refined to fit field breakthrough curves. The model and the lab results indicated that formate-enhanced nitrite reduction was nearly 4-fold slower than nitrate reduction, but in the lab, nitrite was completely consumed with sufficient exposure time. Results of this study suggest that a long-term injection of formate is necessary to test the remediation potential of this approach for nitrate contamination and that adaptation to nitrite accumulation will be a key determinative factor.     

Investigation of chromate coordination on ferrihydrite by in situ ATR-FTIR spectroscopy and theoretical frequency calculations

Chromate mobility, reactivity, and bioavailability in soil environments are affected by adsorption reactions on iron oxide minerals, but the adsorption mechanisms remain controversial. In this study, we employed in situ attenuated total reflectance Fourier transform infrared spectroscopy and theoretical frequency calculations to characterize chromate adsorption on 2-line ferrihydrite. The effects of pH, aqueous chromate concentration, ionic strength, and deuterium exchange were investigated. Results suggest the formation of monodentate and bidentate surface complexes. It was determined that monodentate complexes are dominant at low surface coverage and pH ≥ 6.5 and that bidentate complexes form at high surface coverage and pH < 6. Deuterium exchange experiments indicated that the inner-sphere complexes are not protonated. Difference spectra revealed that monodentate complexes are particularly susceptible to ionic strength effects under acidic conditions.     

Aquasols: on the role of secondary minima

Experiments are presented that test the hypothesis of deposition into and reentrainment from secondary minima during flow through porous media. The release of deposited particles following a decrease in ionic strength is inconsistent with deposition in the primary minimum of either simple DLVO interaction energy curves (which suggest that deposition is irreversible) or Born-DLVO interaction energy curves (which create a finite primary minimum that deepens with decreasing ionic strength). The observed release of particles is, on the other hand, consistent with deposition in the secondary minimum because this energy minimum decreases and can disappear with decreasing ionic strength. The implications for colloid transport of a reversible deposition process in the secondary minimum are very different from those of a process involving irreversible deposition in the primary minimum. First, particles that are continually captured and released will travel much farther in the subsurface than might be expected if the classic irreversible filtration model is applied. Second, and perhaps more significantly, deposition in the secondary well can increase with increasing particle size. Although particle transport by convective diffusion increases as particle size decreases, particle "attachment" in secondary minima decreases with decreasing particle size. Thus, smaller particles (those with diameters in the order of a few tens of nanometers) would be more effective in the facilitated transport of highly sorbing contaminants such as hydrophobic organic molecules, metals, and radionuclides. Other contaminants are themselves particles, such as viruses (tens of nanometers in diameter) and bacteria (near 1 microm in diameter). Due to this difference in size, viruses could be transported over much larger distances than bacteria. Third, the transport of colloids and, hence, the transport of contaminants associated with them, depends on the Hamaker constant of the particle-water-aquifer media system. Colloids of lower Hamaker constant are likely to be transported farther than colloids of higher Hamaker constant. The extent of adsorption of specific contaminants and the Hamaker constant for the particle-aquifer system are both characteristics of the particles and contribute to the effectiveness of colloid-facilitated transport. Finally, the solution chemistry of the pore waters (through pH, ionic strength, types of solutes, and the valence of the ions) ultimately controls the deposition and release of colloidal particles in porous media. The pH determines the charge density and surface potential of the surfaces. When the surfaces are similarly charged, their interaction can be unfavorable, with an energy barrier and secondary minimum. The ionic strength and valence of the ions determines the shape of the interaction energy curve, including the presence and height of the energy barrier and the presence and depth of the secondary well. Since the subsequent release of a particle depends on the mode in which the particle is deposited (primary or secondary), these factors are particularly important in determining the extent of colloid transport in the subsurface.     

In situ mobilization of colloids and transport of cesium in Hanford sediments

Radioactive waste, accumulated during Pu production, has leaked into the subsurface from underground storage tanks at the U.S. Department of Energy's Hanford site. The leaking solutions contained 137Cs and were of high ionic strength. Such a tank leak was simulated experimentally in steady-state flow experiments with packed Hanford sediments. The initial leak was simulated by a 1 M NaNO3 solution, followed by a decrease of ionic strength to 1 mM NaNO3. Cesium breakthrough curves were determined in both 1 M and 1 mM NaNO3 background. Colloidal particles were mobilized during the change of ionic strength. Mobilized colloids consisted mainly of quartz, mica, illite, kaolinite, and chlorite. Electrophoretic mobilities of colloids in the eluent solution were -3(microm/s)(V/cm) and increased to less negative values during later stages of mobilization. Mobilized colloids carried a fraction of the cesium along. While transport of cesium in 1 M NaNO3 background was much faster than in 1 mM NaNO3, cesium attached to colloids moved almost unretarded through the sediments. Cesium attached to mobilized colloids was likely associated with high affinity sorption sites on micas and illites.     

Colloidal stability of carbonate-coated silver nanoparticles in synthetic and natural freshwater

To gain important information on fate, mobility, and bioavailability of silver nanoparticles (AgNP) in aquatic systems, the influence of pH, ionic strength, and humic substances on the stability of carbonate-coated AgNP (average diameter 29 nm) was systematically investigated in 10 mM carbonate and 10 mM MOPS buffer, and in filtered natural freshwater. Changes in the physicochemical properties of AgNP were measured using nanoparticle tracking analysis, dynamic light scattering, and ultraviolet-visible spectroscopy. According to the pH-dependent carbonate speciation, below pH 4 the negatively charged surface of AgNP became positive and increased agglomeration was observed. Electrolyte concentrations above 2 mM Ca(2+) and 100 mM Na(+) enhanced AgNP agglomeration in the synthetic media. In the considered concentration range of humic substances, no relevant changes in the AgNP agglomeration state were measured. Agglomeration of AgNP exposed in filtered natural freshwater was observed to be primarily controlled by the electrolyte type and concentration. Moreover, agglomerated AgNP were still detected after 7 days of exposure. Consequently, slow sedimentation and high mobility of agglomerated AgNP could be expected under the considered natural conditions. A critical evaluation of the different methods used is presented as well.     

离子强度对乌鳢胶原蛋白短肽聚集结构及理化特性的作用

为了研究乌鳢胶原肽在6种不同离子强度诱导下聚集的结构与特性的变化规律,对聚集体变化过程中的内源荧光、浊度、微观结构、粒径、黏度及其二级结构进行测定。结果表明,在0～500 mM的Na Cl范围内,离子强度具有促进胶原蛋白肽自组装聚集的效果,且聚集速率随离子强度的增大而增加。在0～150 mM范围内,胶原蛋白肽聚集的三维网络紧密性增加,聚集体平均粒径增大74.42%,最大剪切黏度增加487.67%。当离子强度在150～500 mM范围时,胶原蛋白肽三维网络紧密性降低,聚集体平均粒径下降,最大剪切黏度降低21.39%。胶原蛋白肽聚集体的二级结构并没有随离子强度变化而发生明显变化。因此,适度的增大样品离子强度可促进胶原肽的自组装聚集,改善其凝胶的三维网络结构和理化特性,为胶原蛋白肽进一步应用于制备药物载体的研究提供参考。     

In situ colloid mobilization in Hanford sediments under unsaturated transient flow conditions: effect of irrigation pattern

Colloid transport may facilitate off-site transport of radioactive wastes at the Hanford site, Washington State. In this study, column experiments were conducted to examine the effect of irrigation schedule on releases of in situ colloids from two Hanford sediments during saturated and unsaturated transientflow and its dependence on solution ionic strength, irrigation rate, and sediment texture. Results show that transient flow mobilized more colloids than steady-state flow. The number of short-term hydrological pulses was more important than total irrigation volume for increasing the amount of mobilized colloids. This effect increased with decreasing ionic strength. At an irrigation rate equal to 5% of the saturated hydraulic conductivity, a transient multipulse flow in 100 mM NaNO3 was equivalent to a 50-fold reduction of ionic strength (from 100 mM to 2 mM) with a single-pulse flow in terms of their positive effects on colloid mobilization. Irrigation rate was more important for the initial release of colloids. In addition to water velocity, mechanical straining of colloids was partly responsible for the smaller colloid mobilization in the fine than in the coarse sands, although the fine sand contained much larger concentrations of colloids than the coarse sand.     

Transport and deposition of polymer-modified Fe0 nanoparticles in 2-D heterogeneous porous media: effects of particle concentration, Fe0 content, and coatings

Concentrated suspensions of polymer-modified Fe(0) nanoparticles (NZVI) are injected into heterogeneous porous media for groundwater remediation. This study evaluated the effect of porous media heterogeneity and the dispersion properties including particle concentration, Fe(0) content, and adsorbed polymer mass and layer thickness which are expected to affect the delivery and emplacement of NZVI in heterogeneous porous media in a two-dimensional (2-D) cell. Heterogeneity in hydraulic conductivity had a significant impact on the deposition of NZVI. Polymer modified NZVI followed preferential flow paths and deposited in the regions where fluid shear is insufficient to prevent NZVI agglomeration and deposition. NZVI transported in heterogeneous porous media better at low particle concentration (0.3 g/L) than at high particle concentrations (3 and 6 g/L) due to greater particle agglomeration at high concentration. High Fe(0) content decreased transport during injection due to agglomeration promoted by magnetic attraction. NZVI with a flat adsorbed polymeric layer (thickness ～30 nm) could not be transported effectively due to pore clogging and deposition near the inlet, while NZVI with a more extended adsorbed layer thickness (i.e., ～70 nm) were mobile in porous media. This study indicates the importance of characterizing porous media heterogeneity and NZVI dispersion properties as part of the design of a robust delivery strategy for NZVI in the subsurface.     

Influence of collector surface composition and water chemistry on the deposition of cerium dioxide nanoparticles: QCM-D and column experiment approaches

The deposition behavior of cerium dioxide (CeO(2)) nanoparticles (NPs) in dilute NaCl solutions was investigated as a function of collector surface composition, pH, ionic strength, and organic matter (OM). Sensors coated separately with silica, iron oxide, and alumina were applied in quartz crystal microbalance with dissipation (QCM-D) to examine the effect of these mineral phases on CeO(2) deposition in NaCl solution (1-200 mM). Frequency and dissipation shift followed the order: silica > iron oxide > alumina in 10 mM NaCl at pH 4.0. No significant deposition was observed at pH 6.0 and 8.5 on any of the tested sensors. However, ≥ 94.3% of CeO(2) NPs deposited onto Ottawa sand in columns in 10 mM NaCl at pH 6.0 and 8.5. The inconsistency in the different experimental approaches can be mainly attributed to NP aggregation, surface heterogeneity of Ottawa sand, and flow geometry. In QCM-D experiments, the deposition kinetics was found to be qualitatively consistent with the predictions based on the classical colloidal stability theory. The presence of low levels (1-6 mg/L) of Suwannee River humic acid, fulvic acid, alginate, citric acid, and carboxymethyl cellulose greatly enhanced the stability and mobility of CeO(2) NPs in 1 mM NaCl at pH 6.5. The poor correlation between the transport behavior and electrophoretic mobility of CeO(2) NPs implies that the electrosteric effect of OM was involved.     

Transport of fullerene nanoparticles (nC60) in saturated sand and sandy soil: controlling factors and modeling

Understanding subsurface transport of fullerene nanoparticles (nC(60)) is of critical importance for the benign use and risk management of C(60). We examined the effects of several important environmental factors on nC(60) transport in saturated porous media. Decreasing flow velocity from approximately 10 to 1 m/d had little effect on nC(60) transport in Ottawa sand (mainly pure quartz), but significantly inhibited the transport in Lula soil (a sandy, low-organic-matter soil). The difference was attributable to the smaller grain size, more irregular and rougher shape, and greater heterogeneity of Lula soil. Increasing ionic strength and switching background solution from NaCl to CaCl(2) enhanced the deposition of nC(60) in both sand and soil columns, but the effects were more significant for soil. This was likely because the clay minerals (and possibly soil organic matter) in soil responded to changes of ionic strength and species differently than quartz. Anions in the mobile phase had little effect on nC(60) transport, and fulvic acid in the mobile phase (5.0 mg/L) had a small effect in the presence of 0.5 mM Ca(2+). A two-site transport model that takes into account both the blocking-affected attachment process and straining effects can effectively model the breakthrough of nC(60).     

Arsenic mobilization through microbially mediated deflocculation of ferrihydrite

This study examined the potential impact of microbially mediated reduction of Fe in the Fe(III)-(hydr)oxide mineral ferrihydrite on the mobility of As in natural waters. In microcosm experiments, the obligately anaerobic bacterium Geobacter metallireducens reduced on average 10% of the Fe(III) in ferrihydrite with varying sorbed As(V) surface coverages, which resulted in deflocculation of initially micron-sized As-bearing ferrihydrite aggregates to nanometersized colloids. No reduction of As(V) to As(III) was observed in microcosm samples. Measurement of Fe and As within operationally defined particulate, colloidal, and dissolved fractions of microcosm slurry samples revealed that little Fe or As was released from ferrihydrite as dissolved species. Microbially induced deflocculation of ferrihydrite in the presence of G. metallireducens was correlated with more negative zeta potential of ferrihydrite nanoparticles suggesting that G. metallireducens mediated As mobilization through alteration of ferrihydrite surface charge. TEM analysis and solution chemistry conditions suggested formation of a magnetite surface layer through topotactic recrystallization of ferrihydrite (2LFH) driven by sorbed Fe(II). The formation of nanometer-sized As-bearing colloids through microbially mediated reduction of Fe-(hydr)oxides has the potential to increase human As exposure by enhancing As mobility in natural waters and hindering As removal during subsequent drinking water treatment.     

Speciation-dependent microbial reduction of uranium within iron-coated sands

Transport of uranium within surface and subsurface environments is predicated largely on its redox state. Uranyl reduction may transpire through either biotic (enzymatic) or abiotic pathways; in either case, reduction of U(VI) to U(IV) results in the formation of sparingly soluble UO2 precipitates. Biological reduction of U(VI), while demonstrated as prolific under both laboratory and field conditions, is influenced by competing electron acceptors (such as nitrate, manganese oxides, or iron oxides) and uranyl speciation. Formation of Ca-UO2-CO3 ternary complexes, often the predominate uranyl species in carbonate-bearing soils and sediments, decreases the rate of dissimilatory U(VI) reduction. The combined influence of uranyl speciation within a mineralogical matrix comparable to natural environments and under hydrodynamic conditions, however, remains unresolved. We therefore examined uranyl reduction by Shewanella putrefaciens within packed mineral columns of ferrihydrite-coated quartz sand under conditions conducive or nonconducive to Ca-UO2-CO3 species formation. The results are dramatic. In the absence of Ca, where uranyl carbonato complexes dominate, U(VI) reduction transpires and consumes all of the U(VI) within the influent solution (0.166 mM) over the first 2.5 cm of the flow field for the entirety of the 54 d experiment. Over 2 g of U is deposited during this reaction period, and despite ferrihydrite being a competitive electron acceptor, uranium reduction appears unabated for the duration of our experiments. By contrast, in columns with 4 mM Ca in the influent solution (0.166 mM uranyl), reduction (enzymatic or surface-bound Fe(III) mediated) appears absent and breakthrough occurs within 18 d (at a flow rate of 3 pore volumes per day). Uranyl speciation, and in particular the formation of ternary Ca-UO2-CO3 complexes, has a profound impact on U(VI) reduction and thus transport within anaerobic systems.     

Thermodynamic constraints on the oxidation of biogenic UO2 by Fe(III) (Hydr)oxides

Uranium mobility in the environment is partially controlled by its oxidation state, where it exists as either U(VI) or U(IV). In aerobic environments, uranium is generally found in the hexavalent form, is quite soluble, and readily forms complexes with carbonate and calcium. Under anaerobic conditions, common metal respiring bacteria can reduce soluble U(VI) species to sparingly soluble UO2 (uraninite); stimulation of these bacteria, in fact, is being explored as an in situ uranium remediation technique. However, the stability of biologically precipitated uraninite within soils and sediments is not well characterized. Here we demonstrate that uraninite oxidation by Fe(III) (hydr)oxides is thermodynamically favorable under limited geochemical conditions. Our analysis reveals that goethite and hematite have a limited capacity to oxidize UO2(biogenic) while ferrihydrite can lead to UO2(biogenic) oxidation. The extent of UO2(biogenic) oxidation by ferrihydrite increases with increasing bicarbonate and calcium concentration, but decreases with elevated Fe(II)(aq) and U(VI)(aq) concentrations. Thus, our results demonstrate that the oxidation of UO2(biogenic) by Fe(III) (hydr)oxides may transpire under mildly reducing conditions when ferrihydrite is present.