Reductive removal of pertechnetate and chromate by zero valent iron under variable ionic strength conditions.

Radioactive technetium-99 (Tc) present in waste streams and subsurface plumes at legacy nuclear reprocessing sites worldwide poses potential risks to human health and environment. This research comparatively evaluated efficiency of zero-valent iron (ZVI) toward reductive removal of Tc(VII) in presence of Cr(VI) from NaCl and Na2SO4 electrolyte solutions under ambient atmospheric conditions. In both electrolytes, anticorrosive Cr(VI) suppressed oxidation of ZVI at elevated concentrations resulting in the delay of initiation of Tc(VII) reduction to Tc(IV). In the absence of Cr(VI), no delay was observed in the analogous systems. At low ionic strength (IS), retarded ZVI oxidation inhibited Tc(VII) reduction. Higher IS favored reduction of both Tc(VII) and Cr(VI), which followed second-order reaction rates in both electrolytes attributed to the more efficient iron oxidation as evident from solids characterization studies. Magnetite was the primary iron oxide phase, and its higher fraction in the SO42- solutions facilitated reductive removal of Tc(VII) and Cr(VI). In the Cl- matrix, Cr(VI) promoted further oxidation of magnetite as well as formation of chromite diminishing overall reductive capacity of this system and resulting in less effective removal of Tc(VII) compared to the SO42- solutions.

Solid phase characterization and transformation of illite mineral with gas-phase ammonia treatment.

In situ remediation applications of ammonia (NH3) gas have potential for sequestration of subsurface contamination. Ammonia gas injections initially increase the pore water pH leading to mineral dissolution followed by formation of secondary precipitates as the pH is neutralized. However, there is a lack of understanding of fundamental alteration processes due to NH3 treatment. In these batch studies, phyllosilicate minerals (illite and montmorillonite) were exposed to NH3 gas with subsequent aeration to simulate in situ remediation. Following treatments, solids were characterized using a variety of techniques, including X-ray diffraction, N2 adsorption-desorption analysis for surface area, Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), and microscopy methods to investigate physicochemical transformations. Results indicate that, at high pH, the clays are altered as observed by differences in morphology and particle size via microscopy. However, the two clays interact differently with NH3. While montmorillonite interlayers collapsed due to intercalation, illite layers were unaffected as confirmed by FTIR analysis. Further, structural changes in silicate ([SiO4]n-) and aluminol (Al-OH) groups were identified by NMR and FTIR. This research showed that mineral alteration processes occur during and after NH3 gas treatment which may be used to remove radionuclides from the aqueous phase through sorption, co-precipitation, and coating with secondary phyllosilicate alteration products.

Time dependent zero valent iron oxidation and the reductive removal of pertechnetate at variable pH.

Elemental iron Fe0 is a promising reductant for removal of radioactive technetium-99 (Tc) from complex aqueous waste streams that contain sulfate, halides, and other inorganic anions generated during processing of legacy radioactive waste. The impact of sulfate on the kinetics of oxidation and reduction capacity of Fe0 in the presence of Tc has not been examined. We investigated the oxidative transformation of Fe0 and reductive removal of TcO4- in 0.1 M Na2SO4 as a function of initial pH (i.e., pHi 4, 7, and 10) under aerobic conditions up to 30 days. Tc reduction was the fastest at pHi 7 and slowest at pHi 10 (Tc reduction rate pHi 7 > 4 > 10). Aqueous fraction of Tc was measured at 0.4% at pHi 7 within 6 h, whereas ≥ 97% of Tc was removed from solutions at pHi of 4 and 10 within 24 h. Solid phase characterization showed that magnetite was the only oxidized crystalline phase for the first 6 h regardless of initial pH. Lepidocrocite was the most abundant oxidized product for pHi 10 after 5 days, but was not observed at pH of 4 or 7.

Spontaneous redox continuum reveals sequestered technetium clusters and retarded mineral transformation of iron.

The sequestration of metal ions into the crystal structure of minerals is common in nature. To date, the incorporation of technetium(IV) into iron minerals has been studied predominantly for systems under carefully controlled anaerobic conditions. Mechanisms of the transformation of iron phases leading to incorporation of technetium(IV) under aerobic conditions remain poorly understood. Here we investigate granular metallic iron for reductive sequestration of technetium(VII) at elevated concentrations under ambient conditions. We report the retarded transformation of ferrihydrite to magnetite in the presence of technetium. We observe that quantitative reduction of pertechnetate with a fraction of technetium(IV) structurally incorporated into non-stoichiometric magnetite benefits from concomitant zero valent iron oxidative transformation. An in-depth profile of iron oxide reveals clusters of the incorporated technetium(IV), which account for 32% of the total retained technetium estimated via X-ray absorption and X-ray photoelectron spectroscopies. This corresponds to 1.86 wt.% technetium in magnetite, providing the experimental evidence to theoretical postulations on thermodynamically stable technetium(IV) being incorporated into magnetite under spontaneous aerobic redox conditions.

Biotic dissolution of autunite under anaerobic conditions: effect of bicarbonates and Shewanella oneidensis MR1 microbial activity.

Uranium is a contaminant of major concern across the US Department of Energy complex that served a leading role in nuclear weapon fabrication for half a century. In an effort to decrease the concentration of soluble uranium, tripolyphosphate injections were identified as a feasible remediation strategy for sequestering uranium in situ in contaminated groundwater at the Hanford Site. The introduction of sodium tripolyphosphate into uranium-bearing porous media results in the formation of uranyl phosphate minerals (autunite) of general formula {X1-2[(UO2)(PO4)]2-1·nH2O}, where X is a monovalent or divalent cation. The stability of the uranyl phosphate minerals is a critical factor that determines the long-term effectiveness of this remediation strategy that can be affected by biogeochemical factors such as the presence of bicarbonates and bacterial activity. The objective of this research was to investigate the effect of bicarbonate ions present in the aqueous phase on Ca-autunite dissolution under anaerobic conditions, as well as the role of metal-reducing facultative bacterium Shewanella oneidensis MR1. The concentration of total uranium determined in the aqueous phase was in direct correlation to the concentration of bicarbonate present in the solution, and the release of Ca, U and P into the aqueous phase was non-stoichiometric. Experiments revealed the absence of an extensive biofilm on autunite surface, while thermodynamic modeling predicted the presence of secondary minerals, which were identified through microscopy. In conclusion, the dissolution of autunite under the conditions studied is susceptible to bicarbonate concentration, as well as microbial presence.

Comparative analysis of ZVI materials for reductive separation of 99Tc(VII) from aqueous waste streams.

Technetium-99 (Tc) is a long-lived radioactive contaminant present in legacy nuclear waste streams and contaminated plumes of the nuclear waste storage sites worldwide that poses risks for human health and the environment. Pertechnetate (TcO4-), the most common chemical form of Tc under oxidative conditions, is of particular concern due to its high aqueous solubility and mobility in the subsurface. One approach to treatment and remediation of TcO4- is reduction of Tc7+ to less soluble and mobile Tc4+ and its removal from the contaminated streams such as liquid secondary waste generated during vitrification of the Hanford low activity tank waste. Zero valent iron (ZVI) is a common reactive agent for reductive treatment of environmental contaminants, including reducible heavy metal ions, which can offer a potential solution to this challenge. Here, we present a comparative study of eleven commercial ZVI materials manufactured by different methods that were evaluated for the reductive removal of TcO4- from an aqueous 80 mM NaCl solution at near neutral pH representing low activity waste off-gas condensate. Performance of ZVI materials was analyzed in relation to time-dependent Fe2+ dissolution as well as pH and ORP profiles of the contact solution. Large variability in the efficiency and kinetics of Tc7+ reduction by different ZVI materials was contingent on their origin. ZVI materials manufactured by electrolytic method exhibited superior performance, and the kinetics of the Tc7+ reduction correlated to particle size. ZVI materials manufactured by iron pentacarbonyl reduction with hydrogen were ineffective for Tc7+ reduction. In general, our results highlight the need for thorough performance analysis of commercial ZVI materials for any contaminant of interest.

Potential for U sequestration with select minerals and sediments via base treatment.

Temporary base treatment is a potential remediation technique for heavy metals through adsorption, precipitation, and co-precipitation with minerals. Manipulation of pH with ammonia gas injection may be especially useful for vadose zone environments as it does not require addition of liquids that would increase the flux towards groundwater. In this research, we conducted laboratory batch experiments to evaluate the changes in uranium mobility and mineral dissolution with base treatments including sodium hydroxide, ammonium hydroxide, and ammonia gas. Our data show that partitioning of uranium to the solid phase increases by several orders of magnitude following base treatment in the presence of different minerals and natural sediments from the Hanford site. The presence of dissolved calcium and carbonate play an important role in precipitation and co-precipitation of uranium at elevated pH. In addition, significant incongruent dissolution of bulk mineral phases occurs and likely leads to precipitation of secondary mineral phases. These secondary phases may remove uranium via adsorption, precipitation, and co-precipitation processes and may coat uranium phases with low solubility minerals as the pH returns to natural conditions.

Quantification of kinetic rate law parameters for the dissolution of natural autunite in the presence of aqueous bicarbonate ions at high concentrations.

Uranium is a key contaminant of concern in the groundwater at U.S. Department of Energy (DOE) facilities within the United States and is a potential source of groundwater contamination and a risk to human health and the environment through discharges to surface water. Dissolved inorganic carbon (bicarbonate/carbonate) has a high affinity for complexing with uranium that is present as sorbed or unique uranium-bearing mineral phases within the sedimentary matrix. This process can result in the formation of soluble uranyl carbonate aqueous species, which are mobile under circumneutral pH conditions. This study was conducted to quantify the rate of release of uranium from the autunite mineral, (Ca[(UO2)(PO4)]2•3H2O), that was formed during polyphosphate injection to remediate uranium; the dissolution of uranium was studied as a function of the aqueous bicarbonate concentration, ranging from 25 to 100 mM. Experiments were carried out in the pH range from 7 to 11 in the temperature range of 23-90 °C via single-pass flow-through testing. Consistent with the results of previous studies (Gudavalli et al., 2013a, 2013b), the rate of uranium release from autunite exhibited minimal dependency on temperature, but was strongly dependent on pH and increasing concentrations of bicarbonate in the solution. Data obtained during these experiments were compared with results of previous experiments conducted using a low-concentration range of bicarbonate solutions (0.5-3.0 mM). An 8- to 30-fold increase in the rate of uranium release was observed in the presence of high bicarbonate concentrations at pH 7-8 compared to low bicarbonate values, while at pH 9-11, there was only a 5-fold increase in uranium rate of release with an increase in bicarbonate concentrations. The rate of uranium release was calculated to be between 5.18 × 10-8 and 1.69 × 10-7 mol m-2 s-1. The activation energy values at high and low bicarbonate concentrations were similar, with ratio values in the range of 0.6-1.0.

Unrefined humic substances as a potential low-cost amendment for the management of acidic groundwater contamination.

The present study explores a novel application of Huma-K, a commercially available, unrefined humic substance, as a promising low-cost source of organic matter for in situ remediation of contaminated acidic groundwater plumes. This can be achieved by creating a humic-rich coating on the surface of minerals which can enhance the sorption of contaminants from groundwater. Huma-K was characterized by means of scanning electron microscopy equipped with energy dispersive spectroscopy, Fourier-transform infrared analysis, and potentiometric titrations. Batch experiments were performed to investigate the sorption-desorption behavior of Huma-K and to evaluate what conditions (pH, contact time, and initial Huma-K concentration) affect these processes upon injection into aquifer sediments. As evidenced by potentiometric titrations, Huma-K possesses functional groups that have an acidic nature, with pK values in the range of 4-6 (carboxylic) and 9-10 (phenolic). Sorption, homogeneous precipitation, and surface-induced precipitation seem to be favored in the presence of sediment at pH 4, where there is less deprotonation of acidic functional groups. As the pH is increased, functional groups become negatively charged, leading to electrostatic repulsion and dissolution of Huma-K from sediment. Kinetic experiments indicate that Huma-K sorption is a slow-rate process, most likely governed by film diffusion. The enhanced sorption of Huma-K in acidic conditions suggests that it may be used to create a subsurface treatment zone in acidic aquifers for the sequestration of contaminants such as uranium. The treatment zone will persist as long as the pH does not increase sufficiently to cause soil-bound Huma-K to be released, remobilizing aqueous contaminants.

Effects of ammonium on uranium partitioning and kaolinite mineral dissolution.

Ammonia gas injection is a promising technique for the remediation of uranium within the vadose zone. It can be used to manipulate the pH of a system and cause co-precipitation processes that are expected to remove uranium from the aqueous phase and decrease leaching from the solid phase. The work presented in this paper explores the effects of ammonium and sodium hydroxide on the partitioning of uranium and dissolution of the kaolinite mineral in simplified synthetic groundwaters using equilibrium batch sorption and sequential extraction experiments. It shows that there is a significant increase in uranium removal in systems with divalent cations present in the aqueous phase but not in sodium chloride synthetic groundwaters. Further, the initial conditions of the aqueous phase do not affect the dissolution of kaolinite. However, the type of base treatment does have an effect on mineral dissolution.

The effect of bicarbonate on the microbial dissolution of autunite mineral in the presence of gram-positive bacteria.

Bacteria are key players in the processes that govern fate and transport of contaminants. The uranium release from Na and Ca-autunite by Arthrobacter oxydans strain G968 was evaluated in the presence of bicarbonate ions. This bacterium was previously isolated from Hanford Site soil and in earlier prescreening tests demonstrated low tolerance to U(VI) toxicity compared to other A. oxydans isolates. Experiments were conducted using glass serum bottles as mixed bioreactors and sterile 6-well cell culture plates with inserts separating bacteria cells from mineral solids. Reactors containing phosphorus-limiting media were amended with bicarbonate ranging between 0 and 10 mM and meta-autunite solids to provide a U(VI) concentration of 4.4 mmol/L. Results showed that in the presence of bicarbonate, A. oxydans G968 was able to enhance the release of U(VI) from Na and Ca autunite at the same capacity as other A. oxydans isolates with relatively high tolerance to U(VI). The effect of bacterial strains on autunite dissolution decreases as the concentration of bicarbonate increases. The results illustrate that direct interaction between the bacteria and the mineral is not necessary to result in U(VI) biorelease from autunite. The formation of secondary calcium-phosphate mineral phases on the surface of the mineral during the dissolution can ultimately reduce the natural autunite mineral contact area, which bacterial cells can access. This thereby reduces the concentration of uranium released into the solution. This study provides a better understanding of the interactions between meta-autunite and microbes in conditions mimicking arid and semiarid subsurface environments of western U.S.

The effect of uranium on bacterial viability and cell surface morphology using atomic force microscopy in the presence of bicarbonate ions.

Past disposal practices at nuclear production facilities have led to the release of liquid waste into the environment creating multiple radionuclide plumes. Microorganisms are known for the ability to interact with radionuclides and impact their mobility in soils and sediments. Gram-positive Arthrobacter sp. are one of the most common bacterial groups in soils and are found in large numbers in subsurface environments contaminated with radionuclides. This study experimentally analyzed changes on the bacteria surface at the nanoscale level after uranium exposure and evaluated the effect of aqueous bicarbonate ions on U(VI) toxicity of a low uranium-tolerant Arthrobacter oxydans strain G968 by investigating changes in adhesion forces and cell dimensions via atomic force microscopy (AFM). Experiments were extended to assess cell viability by the Live/Dead BacLight Bacterial Viability Kit (Molecular Probes) and quantitatively illustrate the effect of uranium exposure in the presence of varying concentrations of bicarbonate ions. AFM and viability studies showed that samples containing bicarbonate were able to withstand uranium toxicity and remained viable. Samples containing no bicarbonate exhibited deformed surfaces and a low height profile, which, in conjunction with viability studies, indicated that the cells were not viable.

Highly organic natural media as permeable reactive barriers: TCE partitioning and anaerobic degradation profile in eucalyptus mulch and compost.

Batch and column experiments were conducted with eucalyptus mulch and commercial compost to evaluate suitability of highly organic natural media to support anaerobic decomposition of trichloroethylene (TCE) in groundwater. Experimental data for TCE and its dechlorination byproducts were analyzed with Hydrus-1D model to estimate the partitioning and kinetic parameters for the sequential dechlorination reactions during TCE decomposition. The highly organic natural media allowed development of a bioactive zone capable of decomposing TCE under anaerobic conditions. The first order TCE biodecomposition reaction rates were 0.23 and 1.2d(-1) in eucalyptus mulch and compost media, respectively. The retardation factors in the eucalyptus mulch and compost columns for TCE were 35 and 301, respectively. The results showed that natural organic soil amendments can effectively support the anaerobic bioactive zone for remediation of TCE contaminated groundwater. The natural organic media are effective environmentally sustainable materials for use in permeable reactive barriers.

Nanomedicine: magnetic nanoparticles and their biomedical applications.

During this past decade, science and engineering have seen a rapid increase in interest for nanoscale materials with dimensions less than 100 nm, which lie in the intermediate state between atoms and bulk (solid) materials. Their attributes are significantly altered relative to the corresponding bulk materials as they exhibit size dependent behavior such as quantum size effects (depending on bulk Bohr radius), optical absorption and emission, coulomb staircase behavior (electrical transport), superparamagnetism and various unique properties. They are active components of ferrofluids, recording tape, flexible disk recording media along with potential future applications in spintronics: a new paradigm of electronics utilizing intrinsic charge and spin of electrons for ultra-high-density data storage and quantum computing. They are used in a gamut of biomedical applications: bioseparation of biological entities, therapeutic drugs and gene delivery, radiofrequency-induced destruction of cells and tumors (hyperthermia), and contrast-enhancement agents for magnetic resonance imaging (MRI). The magnetic nanoparticles have optimizable, controllable sizes enabling their comparison to cells (10-100 µm), viruses (20-250 nm), proteins (3-50 nm), and genes (10-100 nm). Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Atomic Force Microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) provide necessary characterization methods that enable accurate structural and functional analysis of interaction of the biofunctional particles with the target bioentities. The goal of the present discussion is to provide a broad review of magnetic nanoparticle research with a special focus on the synthesis, functionalization and medical applications of these particles, which have been carried out during the past decade, and to examine several prospective directions.

Evaluation of nanoscale zerovalent iron particles for trichloroethene degradation in clayey soils.

The longevity and reactivity of nanoscale zerovalent iron (nZVI) and palladized bimetallic particles (BNP) were evaluated in batch and column experiments for remediation of a trichloroethene (TCE)-contaminated plume within a clayey soil from Oak Ridge Reservation (ORR). Comparative studies assessing the viability of BNP and nZVI confirmed that particle behavior is severely affected by clay sediments. Surface morphology and composition analyses using SEM and SEM-energy-dispersive spectroscopy spectrum revealed particle agglomeration through the formation of clay-iron aggregates of greater mass during the early phase of the experiment. Batch study results suggest that TCE degradation in ORR clayey soil follows a pseudo-first-order kinetic model exhibiting reaction rate constants (k) of 0.05-0.24 day(-1) at varied iron-to-soil ratios. Despite high reactivity in water, BNP were less effective in the site-derived clay sediment with calculated TCE removal efficiencies of 98.7% and 19.59%, respectively. A column experiment was conducted to investigate particle longevity and indicator parameters of the TCE degradation process under flow conditions. It revealed that the TCE removal efficiency gradually declined over the course of the experiment from 86-93% to 51-52%, correlating to a progressive increase in oxidation-reduction potential (ORP) from -485 to -250 mV and pH drop from 8.2-8.6 to 7.4-7.5. The rate of nZVI deactivation reaction was found to be a first order with a k(d) value of 0.0058 day(-1). SEM images of residual nZVI revealed heavily agglomerated particles. However, despite widespread oxidation and agglomeration, particles managed to maintain some capacity for oxidation. A quantitative analysis of nZVI deactivation has the potential of predicting nZVI longevity in order to improve the design strategy of TCE remediation.