Yelena Katsenovich

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.

Assessment of the Resistance to Uranium (VI) Exposure by Arthrobacter sp. Isolated from Hanford Site Soil

Production of nuclear fuel has resulted in hazardous waste streams that have contaminated the soil and groundwater. Arthrobacter strains, G975, G968, and G954 were used in the prescreening tests to evaluate their tolerance to UO2 2+ and investigate bacteria-U(VI) interactions under oxidizing pH-neutral conditions. Experiments have shown G975 is the fastest growing and the most uranium tolerant strain that removed about 90% of uranium from growth media. Atomic Force Microscopy images exhibited an irregular surface structure, which perhaps provided a larger surface area for uranium precipitation. The data indicate that aerobic heterotrophic bacteria may offer a solution to sequestering uranium in oxic conditions, which prevail in the vadose zone.

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.

Enhancement of TCE Attenuation in Soils by Natural Amendments

The objective of this study was to identify low-cost natural amendments that could be used as carbon sources and sustain a bioactive zone to promote biodegradation of TCE in contaminated shallow groundwater. The natural amendments were compared based on their geophysical characteristics as well as TCE adsorption capacities. The amendments studied included low-cost natural and agricultural materials such as eucalyptus tree mulch, pine bark mulch, muck from the Florida Everglades, SRS wetland peat, commercial compost, and peat humus. These natural substrates have relatively high organic fractions that can retard the movement of TCE while serving as carbon sources. Batch sorption studies were conducted to determine the sorption and retardation characteristics of the amendments for TCE. The experimental results were analyzed in relation to the geophysical characteristics of the amendments and compared with those of natural soils.

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.

Using Nano-sensors in Environmental Radionuclide Monitoring

Radionuclides such as uranium tend to be a pervasive contaminant and can easily migrate due to dissolution in the groundwater of a particular region. It is absorbed through the intestine or lungs and deposited in the tissues, predominantly kidney and bone and is carcinogenic. Toxic effects are seen on the cardiovascular system, liver, muscle, renal and nervous system as well. The existing monitoring methods require manual sample collection and laboratory analysis. In order to monitor the uranium concentration, a novel, specific, sensitive and reproducible uranyl nano-sensor system has been developed. It is made up of functionalized superparamagnetic core-shell magnetic nanoparticles that use an external magnetic field for detection and removal of the analyte from the surrounding aqueous media. The redox properties of the analyte are exploited for enumeration of variables by electrochemical and spectroscopic techniques. In addition, the sensing capabilities can be successfully extended for other heavy metals to obtain a versatile response.

Quantification of kinetic rate law parameters of uranium release from sodium autunite as a function of aqueous bicarbonate concentrations

Environmental context Uranium is a key contaminant of concern because of its high persistence in the environment and toxicity to organisms. The bicarbonate ion is an important complexing agent for uranyl ions and one of the main variables affecting its dissolution. Results from this investigation provide rate law parameters for the dissolution kinetics of synthetic sodium autunite that can influence uranium mobility in the subsurface. Abstract Hydrogen carbonate (also known as bicarbonate) is one of the most significant components within the uranium geochemical cycle. In aqueous solutions, bicarbonate forms strong complexes with uranium. As such, aqueous bicarbonate may significantly increase the rate of uranium release from uranium minerals. Quantifying the relationship of aqueous bicarbonate solutions to the rate of uranium release during dissolution is critical to understanding the long-term fate of uranium within the environment. Single-pass flow-through experiments were conducted to estimate the rate of uranium release from Na meta-autunite as a function of bicarbonate solutions (0.0005–0.003M) over the pH range of 6–11 and temperatures of 5–60°C. Consistent with the results of previous investigations, the rate of uranium release from sodium autunite exhibited minimal dependency on temperature, but was strongly dependent on pH and increasing concentrations of bicarbonate solutions. Most notably at pH 7, the rate of uranium release exhibited a 370-fold increase relative to the rate of uranium release in the absence of bicarbonate. However, the effect of increasing concentrations of bicarbonate solutions on the release of uranium was significantly less under higher pH conditions. It is postulated that at high pH values, surface sites are saturated with carbonate, thus the addition of more bicarbonate would have less effect on uranium release. Results indicate that the activation energies were unaffected by temperature and bicarbonate concentration variations, but were strongly dependent on pH conditions. As the pH increased from 6 to 11, the activation energy values were observed to decrease from 29.94 to 13.07kJmol–1. The calculated activation energies suggest a surface controlled dissolution mechanism.

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.

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.

Retention of neodymium by dolomite at variable ionic strength as probed by batch and column experiments

The results presented in this paper highlight the complexity of adsorption and incorporation processes of Nd with dolomite and significantly improve upon previous work investigating trivalent actinide and lanthanide interactions with dolomite. Both batch and mini column experiments were conducted at variable ionic strength. These data highlight the strong chemisorption of Nd to the dolomite surface (equilibrium Kds > 3000 mL/g) and suggest that equilibrium adsorption processes may not be affected by ionic strength based on similar results at 0.1 and 5.0 M ionic strength in column breakthrough and equilibrium batch (>5 days) results. Mini column experiments conducted over approximately one year also represent a significant development in measurement of sorption of Nd in the presence of flow as previous large-scale column experiments did not achieve breakthrough likely due to the high loading capacity of dolomite for Nd (up to 240 μg/g). Batch experiments in the absence of flow show that the rate of Nd removal increases with increasing ionic strength (up to 5.0 M) with greater removal at greater ionic strength for a 24 h sampling point. We suggest that the increasing ionic strength induces increased mineral dissolution and re-precipitation caused by changes in activity with ionic strength that lead to increased removal of Nd through co-precipitation processes.