Eric M. Pierce

Rapid Removal of Hg(II) from Aqueous Solutions Using Thiol- Functionalized Zn-Doped Biomagnetite Particles

The surfaces of Zn-doped biomagnetite nanostructured particles were functionalized with (3-mercaptopropyl)trimethoxysilane (MPTMS) and used as a high-capacity and collectable adsorbent for the removal of Hg(II) from water. Fourier transform infrared spectroscopy (FTIR) confirmed the attachment of MPTMS on the particle surface. The crystallite size of the Zn-doped biomagnetite was ∼17 nm, and the thickness of the MPTMS coating was ∼5 nm. Scanning transmission electron microscopy and dynamic light scattering analyses revealed that the particles formed aggregates in aqueous solution with an average hydrodynamic size of 826 ± 32 nm. Elemental analyses indicate that the chemical composition of the biomagnetite is Zn(0.46)Fe(2.54)O(4), and the loading of sulfur is 3.6 mmol/g. The MPTMS-modified biomagnetite has a calculated saturation magnetization of 37.9 emu/g and can be separated from water within a minute using a magnet. Sorption of Hg(II) to the nanostructured particles was much faster than other commercial sorbents, and the Hg(II) sorption isotherm in an industrial wastewater follows the Langmuir model with a maximum capacity of ∼416 mg/g, indicating two -SH groups bonded to one Hg. This new Hg(II) sorbent was stable in a range of solutions, from contaminated water to 0.5 M acid solutions, with low leaching of Fe, Zn, Si, and S (<10%).

300 Area Uranium Leach and Adsorption Project

The objective of this study was to measure the leaching and adsorption characteristics of uranium in six near-surface sediment samples collected from the 300 Area of the Hanford Site. Scanning electron micrographs of the samples showed that the uranium contamination in the sediments is most likely present as co-precipitates and/or discrete uranium particles. Molecular probe techniques also confirm the presence of crystalline discrete uranium bearing phases. In all cases, the uranium is present as oxidized uranium (uranyl [U(VI)]). Results from the column leach tests showed that uranium leaching did not follow a constant solubility paradigm. Four of the five contaminated sediments showed a large near instantaneous release of a few percent of the total uranium followed by a slower continual release. Steady-state uranium leachate concentrations were never measured and leaching characteristics and trends were not consistent among the samples. Dissolution kinetics were slow, and the measured leach curves most likely represent a slow kinetically controlled desorption or dissolution paradigm. Batch adsorption experiments were performed to investigate the effect of pH and uranium and carbonate solution concentrations on uranium adsorption onto the uncontaminated sediment. Uranium adsorption Kd values ranged from 0 to > 100 ml/g depending on which solution parameter wasmorexa0» being adjusted. Results of the experiments showed that carbonate solution concentration has the greatest impact on uranium adsorption in the 300 Area. Solution pH was shown to be important in laboratory tests; however, the sediment will dominate the field pH and minimize its overall effect in the 300 Area sediments. Results also showed that uranium sorption onto the background sediment is linear up to uranium concentrations of 3 mg/L, well above the values found in the upper unconfined aquifer. Therefore, the linear Kd model is defensible in predicting the fate of uranium in the 300 Area aquifer.«xa0less

Characterization of soils from an industrial complex contaminated with elemental mercury

Historical use of liquid elemental mercury (Hg(0)l) at the Y-12 National Security Complex in Oak Ridge, TN, USA, resulted in large deposits of Hg(0)l in the soils. The fate and distribution of the spilled Hg(0) are not well characterized. In this study we evaluated analytical tools for characterizing the speciation of Hg in the contaminated soils and then used the analytical techniques to examine the speciation of Hg in two soil cores collected at the site. These include x-ray fluorescence (XRF), soil Hg(0) headspace analysis, and total Hg determination by acid digestion coupled with cold vapor atomic absorption (HgT). XRF was not found to be suitable for evaluating Hg concentrations in heterogeneous soils containing low concentration of Hg or Hg(0) because Hg concentrations determined using this method were lower than those determined by HgT analysis and the XRF detection limit is 20 mg/kg. Hg(0)g headspace analysis coupled with HgT measurements yielded good results for examining the presence of Hg(0)l in soils and the speciation of Hg. The two soil cores are highly heterogeneous in both the depth and extent of Hg contamination, with Hg concentrations ranging from 0.05 to 8400mg/kg. In the first core, Hg(0)l was distributed throughout the 3.2m depth, whereas the second core, from a location 12m away, contained Hg(0)l in a 0.3m zone only. Sequential extractions showed organically associated Hg dominant at depths with low Hg concentration. Soil from the zone of groundwater saturation showed reducing conditions and the Hg is likely present as Hg-sulfide species. At this depth, lateral Hg transport in the groundwater may be a source of Hg detected in the soil at the deeper soil depths. Overall, characterization of soils containing Hg(0)l is difficult because of the heterogeneous distribution of Hg within the soils. This is exacerbated in industrial facilities where fill materials make up much of the soils and historical and continued reworking of the subsurface has remobilized the Hg.

Competitive Incorporation of Perrhenate and Nitrate into Sodalite

Nuclear waste storage tanks at the Hanford site in southeastern Washington have released highly alkaline solutions, containing radioactive and other contaminants, into subsurface sediments. When this waste reacts with subsurface sediments, feldspathoid minerals (sodalite, cancrinite) can form, sequestering pertechnetate (99TcO4-) and other ions. This study investigates the potential for incorporation of perrhenate (ReO4-), a chemical surrogate for 99TcO4-, into mixed perrhenate/nitrate (ReO4-/NO3-) sodalite. Mixed-anion sodalites were hydrothermally synthesized in the laboratory from zeolite A in sodium hydroxide, nitrate, and perrhenate solutions at 90 °C for 24 h. The resulting solids were characterized by bulk chemical analysis, X-ray diffraction, scanning electron microscopy, and X-ray absorption near edge structure spectroscopy (XANES) to determine the products chemical composition, structure, morphology, and Re oxidation state. The XANES data indicated that nearly all rhenium (Re) was incorporated as Re(VII)O4-. The nonlinear increase of the unit cell parameter with ReO4-/NO3- ratios suggests formation of two separate sodalite phases in lieu of a mixed-anion sodalite. The results reveal that the sodalite cage is highly selective toward NO3- over ReO4-. Calculated enthalpy and Gibbs free energy of formation at 298 K for NO3- and ReO4-sodalite suggest that NO3- incorporation into the cage is favored over the incorporation of the larger ReO4-, due to the smaller ionic radius of NO3-. Based on these results, it is expected that NO3-, which is present at significantly higher concentrations in alkaline waste solutions than 99TcO4-, will be strongly preferred for incorporation into the sodalite cage.

Anaerobic Mercury Methylation and Demethylation by Geobacter bemidjiensis Bem.

Microbial methylation and demethylation are two competing processes controlling the net production and bioaccumulation of neurotoxic methylmercury (MeHg) in natural ecosystems. Although mercury (Hg) methylation by anaerobic microorganisms and demethylation by aerobic Hg-resistant bacteria have both been extensively studied, little attention has been given to MeHg degradation by anaerobic bacteria, particularly the iron-reducing bacterium Geobacter bemidjiensis Bem. Here we report, for the first time, that the strain G. bemidjiensis Bem can mediate a suite of Hg transformations, including Hg(II) reduction, Hg(0) oxidation, MeHg production and degradation under anoxic conditions. Results suggest that G. bemidjiensis utilizes a reductive demethylation pathway to degrade MeHg, with elemental Hg(0) as the major reaction product, possibly due to the presence of genes encoding homologues of an organomercurial lyase (MerB) and a mercuric reductase (MerA). In addition, the cells can strongly sorb Hg(II) and MeHg, reduce or oxidize Hg, resulting in both time and concentration-dependent Hg species transformations. Moderate concentrations (10-500 μM) of Hg-binding ligands such as cysteine enhance Hg(II) methylation but inhibit MeHg degradation. These findings indicate a cycle of Hg methylation and demethylation among anaerobic bacteria, thereby influencing net MeHg production in anoxic water and sediments.

In situ remediation technologies for mercury-contaminated soil

Mercury from anthropogenic activities is a pollutant that poses significant risks to humans and the environment. In soils, mercury remediation can be technically challenging and costly, depending on the subsurface mercury distribution, the types of mercury species, and the regulatory requirements. This paper introduces the chemistry of mercury and its implications for in situ mercury remediation, which is followed by a detailed discussion of several in situ Hg remediation technologies in terms of applicability, cost, advantages, and disadvantages. The effect of Hg speciation on remediation performance, as well as Hg transformation during different remediation processes, was detailed. Thermal desorption, electrokinetic, and soil flushing/washing treatments are removal technologies that mobilize and capture insoluble Hg species, while containment, solidification/stabilization, and vitrification immobilize Hg by converting it to less soluble forms. Two emerging technologies, phytoremediation and nanotechnology, are also discussed in this review.

Combined Experimental and Computational Approach to Predict the Glass-Water Reaction

Abstract The use of mineral and glass dissolution rates measured in laboratory experiments to predict the weathering of primary minerals and volcanic and nuclear waste glasses in field studies requires the construction of rate models that accurately describe the weathering process over geologic timescales. Additionally, the need to model the long-term behavior of nuclear waste glass for the purpose of estimating radionuclide release rates requires that rate models be validated with long-term experiments. Several long-term test methods have been developed to accelerate the glass-water reaction [drip test, vapor hydration test, product consistency test B, and pressurized unsaturated flow (PUF)], thereby reducing the duration required to evaluate long-term performance. Currently, the PUF test is the only method that mimics the unsaturated hydraulic properties expected in a subsurface disposal facility and simultaneously monitors the glass-water reaction. PUF tests are being conducted to accelerate the weathering of glass and validate the model parameters being used to predict long-term glass behavior. A one-dimensional reactive chemical transport simulation of glass dissolution and secondary-phase formation during a 1.5-year-long PUF experiment was conducted with the Subsurface Transport Over Reactive Multiphases (STORM) code. Results show that parameterization of the computer model by combining direct benchscale laboratory measurements and thermodynamic data provides an integrated approach to predicting glass behavior over the length of the experiment. Over the 1.5-year-long test duration, the rate decreased from 0.2 to 0.01 g/(m2·day) based on B release for low-activity waste glass LAWA44. The observed decrease is approximately two orders of magnitude higher than the decrease observed under static conditions with the SON68 glass (estimated to be a decrease by four orders of magnitude) and suggests that the gel-layer properties are less protective under these dynamic conditions.

Formation of soluble mercury oxide coatings: transformation of elemental mercury in soils

The impact of mercury (Hg) on human and ecological health has been known for decades. Although a treaty signed in 2013 by 147 nations regulates future large-scale mercury emissions, legacy Hg contamination exists worldwide and small-scale releases will continue. The fate of elemental mercury, Hg(0), lost to the subsurface and its potential chemical transformation that can lead to changes in speciation and mobility are poorly understood. Here, we show that Hg(0) beads interact with soil or manganese oxide solids and X-ray spectroscopic analysis indicates that the soluble mercury coatings are HgO. Dissolution studies show that, after reacting with a composite soil, >20 times more Hg is released into water from the coated beads than from a pure liquid mercury bead. An even larger, >700 times, release occurs from coated Hg(0) beads that have been reacted with manganese oxide, suggesting that manganese oxides are involved in the transformation of the Hg(0) beads and creation of the soluble mercury coatings. Although the coatings may inhibit Hg(0) evaporation, the high solubility of the coatings can enhance Hg(II) migration away from the Hg(0)-spill site and result in potential changes in mercury speciation in the soil and increased mercury mobility.

Understanding the structural drivers governing glass – water interactions in borosilicate based model bioactive glasses

The past decade has witnessed a significant upsurge in the development of borate and borosilicate based resorbable bioactive glasses owing to their faster degradation rate in comparison to their silicate counterparts. However, due to our lack of understanding about the fundamental science governing the aqueous corrosion of these glasses, most of the borate/borosilicate based bioactive glasses reported in the literature have been designed by trial-and-error approach. With an ever-increasing demand for their application in treating a broad spectrum of non-skeletal health problems, it is becoming increasingly difficult to design advanced glass formulations using the same conventional approach. Therefore, a paradigm shift from the trial-and-error approach to materials-by-design approach is required to develop new-generations of bioactive glasses with controlled release of functional ions tailored for specific patients and disease states, whereby material functions and properties can be predicted from first principles. Realizing this goal, however, requires a thorough understanding of the complex sequence of reactions that control the dissolution kinetics of bioactive glasses and the structural drivers that govern them. While there is a considerable amount of literature published on chemical dissolution behavior and apatite-forming ability of potentially bioactive glasses, the majority of this literature has been produced on silicate glass chemistries using different experimental and measurement protocols. It follows that inter-comparison of different datasets reveals inconsistencies between experimental groups. There are also some major experimental challenges or choices that need to be carefully navigated to unearth the mechanisms governing the chemical degradation behavior and kinetics of boron-containing bioactive glasses, and to accurately determine the composition-structure-property relationships. In order to address these challenges, a simplified borosilicate based model melt-quenched bioactive glass system has been studied to depict the impact of thermal history on its molecular structure and dissolution behavior in water. It has been shown that the methodology of quenching of the glass melt impacts the dissolution rate of the studied glasses by 1.5×-3× depending on the changes induced in their molecular structure due to variation in thermal history. Further, a recommendation has been made to study dissolution behavior of bioactive glasses using surface area of the sample - to - volume of solution (SA/V) approach instead of the currently followed mass of sample - to - volume of solution approach. The structural and chemical dissolution data obtained from bioactive glasses following the approach presented in this paper can be used to develop the structural descriptors and potential energy functions over a broad range of bioactive glass compositions.nnnSTATEMENT OF SIGNIFICANCEnRealizing the goal of designing third generation bioactive glasses requires a thorough understanding of the complex sequence of reactions that control their rate of degradation (in physiological fluids) and the structural drivers that control them. In this article, we have highlighted some major experimental challenges and choices that need to be carefully navigated in order to unearth the mechanisms governing the chemical dissolution behavior of borosilicate based bioactive glasses. The proposed experimental approach allows us to gain a new level of conceptual understanding about the composition-structure-property relationships in these glass systems, which can be applied to attain a significant leap in designing borosilicate based bioactive glasses with controlled dissolution rates tailored for specific patient and disease states.

Performance of the Fluidized Bed Steam Reforming Product Under Hydraulically Unsaturated Conditions

Several candidates for supplemental low-activity waste (LAW) immobilization at the Hanford site in Washington State, USA are being considered. One waste sequestering technology considered is Fluidized Bed Steam Reforming (FBSR). The granular product resulting from the FBSR process is composed primarily of an insoluble sodium aluminosilicate matrix with the dominant phases being feldspathoid minerals with a 1:1:1 molar ratio of Na, Al and Si. To demonstrate the durability of the product, which can be disposed of at the unsaturated Integrated Disposal Facility (IDF) at Hanford, a series of tests has been performed using the Pressurized Unsaturated Flow (PUF) system, which allows for the accelerated weathering of the solid materials. The system maintains hydraulically unsaturated conditions, thus mimicking the open-flow and transport properties that will be present at the IDF. Two materials were tested using the system: 1) the FBSR granular product and 2) the FBSR granular product encapsulated in a geopolymer to form a monolith. Results of the experiments show a trend of relatively constant effluent concentration of Na, Si, Al, and Cs as a function of time from both materials. The elements I and Re show a steady release throughout the yearlong test from the granular material but their concentrations seem to be increasing at one year from the monolith material. This result suggests that these two elements may be present in the sodalite cage structure rather than in the predominant nepheline phase because their release occurs at a different rate compared to nepheline phase. Also, these elements to not seem to reprecipitate when released from the starting material. Calculated one-year release rates for Si are on the order of 10(-6)xa0g/(m(2)xa0d) for the granular material and 10(-5)xa0g/(m(2)xa0d) for the monolith material while Re release is seen to be two orders of magnitude higher than Si release rates. SEM imaging and XRD analysis show how the alteration of the two materials is dependent on their depth in the column. This phenomenom is a result of depth-dependent solution concentrations giving rise chemical environments that may be supersaturated with respect to a number of mineral phases.