Accumulation mechanisms for contaminants on weak-base hybrid ion exchange resins.

Mechanism of hexavalent chromium removal (Cr(VI) as CrO) by the weak-base ion exchange (IX) resin ResinTech® SIR-700-HP (SIR-700) from simulated groundwater is assessed in the presence of radioactive contaminants iodine-129 (as IO), uranium (U as uranyl UO), and technetium-99 (as TcO), and common environmental anions sulfate (SO) and chloride (Cl). Batch tests using the acid sulfate form of SIR-700 demonstrated Cr(VI) and U(VI) removal exceeded 97%, except in the presence of high SO concentrations (536 mg/L) where Cr(VI) and U(VI) removal decreased to ≥ 80%. However, Cr(VI) removal notably improved with co-mingled U(VI) that complexes with SO at the protonated amine sites.

Design and Application of Materials for Sequestration and Immobilization of Tc.

Technetium (Tc) is a hazardous radionuclide that poses a serious environmental threat. The wide variation and complex chemistries of liquid nuclear waste streams containing Tc often create unique, site specific challenges when sequestering and immobilizing the waste in a matrix suitable for long-term storage and disposal. Therefore, an effective management plan for Tc containing liquid radioactive wastes (such as storage (tanks) and decommissioned wastes) will likely require a variety of suitable materials/matrixes capable of adapting to and addressing these challenges.

Heteroatom Manipulation of Zeolite Crystallization: Stabilizing Zn-FAU against Interzeolite Transformation.

The preparation of metastable zeolites is often restricted to a limited range of synthesis conditions, which is exemplified in commercial syntheses lacking organics to stabilize the crystal structure. In the absence of an organic structure-directing agent, interzeolite transformation is a common phenomenon that can lead to undesirable products or impurities. Many studies have investigated the substitution of Si and Al in zeolite frameworks with alternative elements (heteroatoms) as a means of tailoring the properties of zeolites; however, relatively few studies have systematically explored the impact of heteroatoms on interzeolite transformations and their concomitant effects on zeolite crystallization.

The evolution of hydrated lime-based cementitious waste forms during leach testing leading to enhanced technetium retention.

The interaction between radionuclides and cementitious material phases is crucial in the prediction of the long-term disposal behavior of cementitious waste forms. This work focuses on the behavior of technetium-99 (Tc) within a hydrated-lime based waste form developed as a candidate to immobilize high-sulphate containing liquid wastes known to inhibit cement solidification when using a fly ash based formulation. In leach testing, the hydrated-lime based formulation demonstrated improvement in Tc retention over a fly ash containing formulation beginning after 14 d leaching.

The behavior of iodine in stabilized granular activated carbon and silver mordenite in cementitious waste forms.

Both granular activated carbon (GAC) and silver mordenite (AgM) are utilized for the removal of contaminants and radionuclides (e.g., radioiodine) from off-gas streams in nuclear fuel reprocessing and high temperature immobilization of nuclear waste.

Metallic technetium sequestration in nickel core/shell microstructure during Fe(OH) transformation with Ni doping.

This study investigates the impacts of Ni doping on technetium-99 (Tc) sequestration in aqueous solutions through transformation of Fe(OH)(s) to iron spinel (magnetite) under alkaline conditions. Extensive solid characterization was performed for the mineral phases produced, as well as the Tc/Ni speciation and distribution within these phases. X-ray diffraction results show that iron spinel was the dominant mineral product without detectable Ni incorporation.

Vanadium Oxidation States and Structural Role in Aluminoborosilicate Glasses: An Integrated Experimental and Molecular Dynamics Simulation Study.

Vanadium-containing glasses have aroused interest in several fields such as electrodes for energy storage, semiconducting glasses, and nuclear waste disposal. The addition of VO, even in small amounts, can greatly alter the physical properties and chemical durability of glasses; however, the structural role of vanadium in these multicomponent glasses and the structural origins of these property changes are still poorly understood. We present a comprehensive study that integrates advanced characterizations and atomistic simulations to understand the composition-structure-property relationships of a series of vanadium-containing aluminoborosilicate glasses.

Resolving Configurational Disorder for Impurities in a Low-Entropy Phase.

Hematite (α-FeO) exerts a strong control over the transport of minor but critical metals in the environment and is used in multiple industrial applications; the photocatalysis community has explored the properties of hematite nanoparticles over a wide range of transition metal dopants. Nonetheless, simplistic assumptions are used to rationalize the local coordination environment of impurities in hematite. Here, we use ab initio molecular dynamics (AIMD)-guided structural analysis to model the extended X-ray absorption fine structure (EXAFS) of Cu- and Zn-doped hematite nanoparticles.

Competitive TcO, IO, and CrO Incorporation into Ettringite.

Ettringite is a naturally occurring mineral found in cementitious matrices that is known for its ability to incorporate environmentally mobile oxyanion contaminants. To better assess this immobilization mechanism for contaminants within cementitious waste forms intended for nuclear waste storage, this work explores how mixed oxyanion contaminants compete for ettringite incorporation and influence the evolving mineralogy. Ettringite was precipitated in the presence of TcO, IO, and/or CrO, known contaminants of concern to nuclear waste treatment, over pre-determined precipitation periods.

Immobilizing Pertechnetate in Ettringite via Sulfate Substitution.

Technetium-99 immobilization in low-temperature nuclear waste forms often relies on additives that reduce environmentally mobile pertechnetate (TcO) to insoluble Tc(IV) species. However, this is a short-lived solution unless reducing conditions are maintained over the hazardous life cycle of radioactive wastes (some ∼10,000 years). Considering recent experimental observations, this work explores how rapid formation of ettringite [CaAl(SO)(OH)·26(HO)], a common mineral formed in cementitious waste forms, may be used to directly immobilize TcO.

Hybrid Sorbents for I Capture from Contaminated Groundwater.

Radioiodine (I) poses a risk to the environment due to its long half-life, toxicity, and mobility. It is found at the U.S.

Technetium immobilization by materials through sorption and redox-driven processes: A literature review.

The objective of this review is to evaluate materials for use as a barrier or other deployed technology to treat technetium-99 (Tc) in the subsurface. To achieve this, Tc interactions with different materials are considered within the context of remediation strategies. Several naturally occurring materials are considered for Tc immobilization, including iron oxides and low solubility sulfide phases.

Iodine immobilization by materials through sorption and redox-driven processes: A literature review.

Radioiodine-129 (I) in the subsurface is mobile and limited information is available on treatment technologies. Scientific literature was reviewed to compile information on materials that could potentially be used to immobilize I through sorption and redox-driven processes, with an emphasis on ex-situ processes. Candidate materials to immobilize I include iron minerals, sulfur-based materials, silver-based materials, bismuth-based materials, ion exchange resins, activated carbon, modified clays, and tailored materials (metal organic frameworks (MOFS), layered double hydroxides (LDHs) and aerogels).

Evaluation of materials for iodine and technetium immobilization through sorption and redox-driven processes.

Radioactive iodine-129 (I) and technetium-99 (Tc) pose a risk to groundwater due to their long half-lives, toxicity, and high environmental mobility. Based on literature reviewed in Moore et al. (2019) and Pearce et al.

Spectroscopic and first-principles investigations of iodine species incorporation into ettringite: Implications for iodine migration in cement waste forms.

Low-level radioactive wastes are commonly immobilized in cementitious materials, where cement-based material can incorporate radionuclides into their crystal structure. Specifically, ettringite (CaAl(OH)(SO)∙26HO) is known to stabilize anionic species, which is appealing for waste streams with radioactive iodine (I) that persists as iodide (I-) and iodate (IO-) in the cementitious nuclear waste repository. However, the structural information and immobilization mechanisms of iodine species in ettringite remain unclear.

Impact of Cr and Co on Tc retention in magnetite: A combined study of ab initio molecular dynamics and experiments.

The effect of co-mingled dopants, Co(II) and Cr(III), on Tc(IV) incorporation and retention in magnetite under varying temperatures (75-700 °C) was explored using ab initio molecular dynamics simulations, batch experiments, and solid phase characterization. Tc(IV) stabilization was achieved with a magnetite surface oversaturated with or containing an equal number of Tc and Cr. Under oversaturation conditions, the forced formation of a CrO phase on the magnetite surface may help prevent Tc release.

Association of Defects and Zinc in Hematite.

Zn is an essential micronutrient that is often limited in tropical, lateritic soils in part because it is sequestered in nominally refractory iron oxide phases. Stable phases such as goethite and hematite, however, can undergo reductive recrystallization without a phase change under circumneutral pH conditions and release metal impurities such as Zn into aqueous solutions. Further, the process appears to be driven by Fe vacancies.

Cr(VI) Effect on Tc-99 Removal from Hanford Low-Activity Waste Simulant by Ferrous Hydroxide.

Here, Cr(VI) effects on Tc-immobilization by Fe(OH)(s) are investigated while assessing Fe(OH)(s) as a potential treatment method for Hanford low-activity waste destined for vitrification. Batch studies using simulated low-activity waste indicate that Tc(VII) and Cr(VI) removal is contingent on reduction to Tc(IV) and Cr(III). Furthermore, complete removal of both Cr and Tc depends on the amount of Fe(OH)(s) present, where complete Cr and Tc removal requires more Fe(OH)(s) (∼200 g/L of simulant), than removing Cr alone (∼50 g/L of simulant).

Facile incorporation of technetium into magnetite, magnesioferrite, and hematite by formation of ferrous nitrate in situ: precursors to iron oxide nuclear waste forms.

The fission product, 99Tc, presents significant challenges to the long-term disposal of nuclear waste due to its long half-life, high fission yield, and to the environmental mobility of pertechnetate (TcO4-), the stable Tc species in aerobic environments. Migration of 99Tc from disposal sites can potentially be prevented by incorporating it into durable waste forms based on environmentally stable minerals. Since Tc(iv) and Fe(iii) have the same ionic radius, Tc(iv) can replace Fe(iii) in iron oxides.

Technetium and iodine aqueous species immobilization and transformations in the presence of strong reductants and calcite-forming solutions: Remedial action implications.

At the Hanford Site in southeastern Washington, discharge of radionuclide laden liquid wastes resulted in vadose zone contamination, providing a continuous source of these contaminants to groundwater. The presence of multiple contaminants (i.e.

Incorporation Modes of Iodate in Calcite.

Iodate (IO) incorporation in calcite (CaCO) is a potential sequestration pathway for environmental remediation of radioiodine-contaminated sites (e.g., Hanford Site, WA), but the incorporation mechanisms have not been fully elucidated.

Experimental Determination of Partitioning in the Fe-Ni System for Applications to Modeling Meteoritic Metals.

Experimental trace element partitioning values are often used to model the chemical evolution of metallic phases in meteorites, but limited experimental data were previously available to constrain the partitioning behavior in the basic Fe-Ni system. In this study, we conducted experiments that produced equilibrium solid metal and liquid metal phases in the Fe-Ni system and measured the partition coefficients of 25 elements. The results are in good agreement with values modeled from IVB iron meteorites and with the limited previous experimental data.

Reduction and Simultaneous Removal of Tc and Cr by Fe(OH)(s) Mineral Transformation.

Technetium (Tc) remains a priority remediation concern due to persistent challenges, including mobilization due to rapid reoxidation of immobilized Tc, and competing comingled contaminants, e.g., Cr(VI), that inhibit Tc(VII) reduction and incorporation into stable mineral phases.

Phase-referenced nonlinear spectroscopy of the α-quartz/water interface.

Probing the polarization of water molecules at charged interfaces by second harmonic generation spectroscopy has been heretofore limited to isotropic materials. Here we report non-resonant nonlinear optical measurements at the interface of anisotropic z-cut α-quartz and water under conditions of dynamically changing ionic strength and bulk solution pH. We find that the product of the third-order susceptibility and the interfacial potential, χ × Φ(0), is given by (χ-iχ) × Φ(0), and that the interference between this product and the second-order susceptibility of bulk quartz depends on the rotation angle of α-quartz around the z axis.

Exponential sensitivity and speciation of Al(III), Sc(III), Y(III), La(III), and Gd(III) at fused silica/water interfaces.

The binding contants, adsorption free energies, absolute adsorbate number densities, and interfacial charge densities of Al(III), Sc(III), Y(III), La(III), and Gd(III) interacting with fused silica/water interfaces held at pH 4 were determined using second harmonic generation and the Eisenthal χ((3)) technique. By examining the relationship between the measured adsorption free energies and the electric double layer interfacial potential at multiple electrolyte concentrations, we elucidate the charge state and possible binding pathways for each ion at the fused silica surface. Al(III) and Sc(III) ions are found to bind to the fused silica surface as fully hydrated trivalent species in a bidentate geometry.