Scale-dependent desorption of uranium from contaminated subsurface sediments

Column experiments were performed to investigate the scale-dependent desorption of uranyl [U(VI)] from a contaminated sediment collected from the Hanford 300 Area at the U.S. Department of Energy (DOE) Hanford Site, Washington. The sediment was a coarse-textured alluvial flood deposit containing significant mass percentage of river cobble. U(VI) was, however, only associated with its minor fine-grained (\u3c2 mm) mass fraction. U(VI) desorption was investigated both from the field-textured sediment using a large column (80 cm length by 15 cm inner diameter) and from its \u3c2 mm U(VI)- associated mass fraction using a small column (10 cm length by 3.4 cm inner diameter). Dynamic advection conditions with intermittent flow and stop-flow events of variable durations were employed to investigate U(VI) desorption kinetics and its scale dependence. A multicomponent kinetic model that integrated a distributed rate of mass transfer with surface complexation reactions successfully described U(VI) release from the fine-grained U(VI)-associated materials. The field-textured sediment in the large column displayed dual-domain tracer-dependent mass transfer properties that affected the breakthrough curves of bromide, pentafluorobenzoic acid (PFBA), and tritium. The tritium breakthrough curve showed stronger nonequilibrium behavior than did PFBA and bromide and required a larger immobile porosity to describe. The dual-domain mass transfer properties were then used to scale the kinetic model of U(VI) desorption developed for the fine-grained materials to describe U(VI) release and reactive transport in the field-textured sediment. Numerical simulations indicated that the kinetic model that was integrated with the dual-domain properties determined from tracer PFBA and Br best described the experimental results. The kinetic model without consideration of the dual-domain properties overpredicted effluent U(VI) concentrations, while the model based on tritium mass transfer underpredicted the rate of U(VI) release. Overall, our results indicated that the kinetics of U(VI) release from the field-textured sediment were different from that of its fine-grained U(VI)-associated mass fraction. However, the desorption kinetics measured on the U(VI)-containing mass fraction could be scaled to describe U(VI) reactive transport in the contaminated field-textured sediment after proper consideration of the physical transport properties of the sediment. The research also demonstrated a modeling approach to integrate geochemical processes into field-scale reactive transport models

Scale-dependent desorption of uranium from contaminated subsurface sediments

Column experiments were performed to investigate the scale-dependent desorption of uranyl [U(VI)] from a contaminated sediment collected from the Hanford 300 Area at the U.S. Department of Energy (DOE) Hanford Site, Washington. The sediment was a coarse-textured alluvial flood deposit containing significant mass percentage of river cobble. U(VI) was, however, only associated with its minor fine-grained (\u3c2 mm) mass fraction. U(VI) desorption was investigated both from the field-textured sediment using a large column (80 cm length by 15 cm inner diameter) and from its \u3c2 mm U(VI)- associated mass fraction using a small column (10 cm length by 3.4 cm inner diameter). Dynamic advection conditions with intermittent flow and stop-flow events of variable durations were employed to investigate U(VI) desorption kinetics and its scale dependence. A multicomponent kinetic model that integrated a distributed rate of mass transfer with surface complexation reactions successfully described U(VI) release from the fine-grained U(VI)-associated materials. The field-textured sediment in the large column displayed dual-domain tracer-dependent mass transfer properties that affected the breakthrough curves of bromide, pentafluorobenzoic acid (PFBA), and tritium. The tritium breakthrough curve showed stronger nonequilibrium behavior than did PFBA and bromide and required a larger immobile porosity to describe. The dual-domain mass transfer properties were then used to scale the kinetic model of U(VI) desorption developed for the fine-grained materials to describe U(VI) release and reactive transport in the field-textured sediment. Numerical simulations indicated that the kinetic model that was integrated with the dual-domain properties determined from tracer PFBA and Br best described the experimental results. The kinetic model without consideration of the dual-domain properties overpredicted effluent U(VI) concentrations, while the model based on tritium mass transfer underpredicted the rate of U(VI) release. Overall, our results indicated that the kinetics of U(VI) release from the field-textured sediment were different from that of its fine-grained U(VI)-associated mass fraction. However, the desorption kinetics measured on the U(VI)-containing mass fraction could be scaled to describe U(VI) reactive transport in the contaminated field-textured sediment after proper consideration of the physical transport properties of the sediment. The research also demonstrated a modeling approach to integrate geochemical processes into field-scale reactive transport models

The Geochemistry of Technetium: A Summary of the Behavior of an Artificial Element in the Natural Environment

Interest in the chemistry of technetium has only increased since its discovery in 1937, mainly because of the large and growing inventory of 99Tc generated during fission of 235U, its environmental mobility in oxidizing conditions, and its potential radiotoxicity. For every ton of enriched uranium fuel (3% 235U) that is consumed at a typical burn-up rate, nearly 1 kg of 99Tc is generated. Thus, the mass of 99Tc produced since 1993 has nearly quadrupled, and will likely to continue to increase if more emphasis is placed on nuclear power to slow the accumulation of atmospheric greenhouse gases. In order to gain a comprehensive understanding of the interaction of 99Tc and the natural environment, we review the sources of 99Tc in the nuclear fuel cycle, its chemical properties, radiochemistry, and biogeochemical behavior. We include an evaluation of the use of Re as a chemical analog of Tc, as well as a summary of the redox potential, thermodynamics, sorption, colloidal behavior, and interaction of humic substances with Tc, and the potential for re-oxidation and remobilization of Tc(IV). What emerges is a more complicated picture of Tc behavior than that of an easily tractable transition of Tc(VII) to Tc(IV) with consequent immobilization. Reducing conditions (+200 to +100 mV Eh) are generally thought necessary to cause reduction of Tc(VII) to Tc(IV), but far more important are the presence of reducing agents, such as Fe(II) sorbed onto mineral grains. Catalysis of Tc(VII) by surface-mediated Fe(II) will bring the mobile Tc(VII) species to a lower oxidation state and will form the relatively insoluble Tc(IV)O2∙nH2O, but even as a solid, equilibrium concentrations of aqueous Tc are nearly a factor of 20× above the EPA set drinking water standards. However, sequestration of Tc(IV) into Fe(III)-bearing phases, such as goethite or other hydrous oxyhydroxides of iron, may ameliorate concerns over the mobility of Tc. Further, the outcome of many studies on terrestrial and marine sediments that are oxidizing overall indicate that Tc is relatively immobile, due to formation of oxygen-depleted microenvironments that develop in response to bacteriological activities. The rate of re-mobilization of Tc from these microenvironments is just beginning to be assessed, but with no firm consensus. Reassessment of the simple models in which Tc is mobilized and immobilized is therefore urged

Chemical weathering of new pyroclastic deposits from Mt. Merapi (Java), Indonesia.

The Java Island, Indonesia with abundant amount of pyroclastic deposits is located in the very active and dynamic Pacific Ring of Fires. Studying the geochemical weathering indices of these pyroclastic deposits is important to get a clear picture about weathering profiles on deposits resulting from the eruption of Mt. Merapi. Immediately after the first phase of the eruption (March to June 2006), moist and leached pyroclastic deposits were collected. These pyroclastic deposits were found to be composed of volcanic glass, plagioclase feldspar in various proportions, orthopyroxene, clinopyroxene, olivine, amphibole and titanomagnetite. The total elemental composition of the bulk samples (including trace elements and heavy metals) was determined by wet chemical methods and X-ray fluorescence (XRF) analyses. Weathering of the pyroclastic deposits was studied using various weathering indices. The Ruxton ratio, weathering index of Parker, Vought resudual index and chemical index of weathering of moist pyroclastic deposits were lower than those of the leached samples, but the alteration indices (chemical and plagioclase) were slightly higher in the moist compared to the leached pyroclastic deposits

Secondary Waste Form Down-Selection Data Package—Fluidized Bed Steam Reforming Waste Form

The Hanford Site in southeast Washington State has 56 million gallons of radioactive and chemically hazardous wastes stored in 177 underground tanks (ORP 2010). The U.S. Department of Energy (DOE), Office of River Protection (ORP), through its contractors, is constructing the Hanford Tank Waste Treatment and Immobilization Plant (WTP) to convert the radioactive and hazardous wastes into stable glass waste forms for disposal. Within the WTP, the pretreatment facility will receive the retrieved waste from the tank farms and separate it into two treated process streams. These waste streams will be vitrified, and the resulting waste canisters will be sent to offsite (high-level waste [HLW]) and onsite (immobilized low-activity waste [ILAW]) repositories. As part of the pretreatment and ILAW processing, liquid secondary wastes will be generated that will be transferred to the Effluent Treatment Facility (ETF) on the Hanford Site for further treatment. These liquid secondary wastes will be converted to stable solid waste forms that will be disposed of in the Integrated Disposal Facility (IDF). To support the selection of a waste form for the liquid secondary wastes from WTP, Washington River Protection Solutions (WRPS) has initiated secondary waste form testing work at Pacific Northwest National Laboratory (PNNL). In anticipation of a down-selection process for a waste form for the Solidification Treatment Unit to be added to the ETF, PNNL is developing data packages to support that down-selection. The objective of the data packages is to identify, evaluate, and summarize the existing information on the four waste forms being considered for stabilizing and solidifying the liquid secondary wastes. At the Hanford Site, the FBSR process is being evaluated as a supplemental technology for treating and immobilizing Hanford LAW radioactive tank waste and for treating secondary wastes from the WTP pretreatment and LAW vitrification processes

Protein–Mineral Interactions: Molecular Dynamics Simulations Capture Importance of Variations in Mineral Surface Composition and Structure

Molecular dynamics simulations, conventional and metadynamics, were performed to determine the interaction of model protein Gb1 over kaolinite (001), Na⁺-montmorillonite (001), Ca²⁺-montmorillonite (001), goethite (100), and Na⁺-birnessite (001) mineral surfaces. Gb1, a small (56 residue) protein with a well-characterized solution-state nuclear magnetic resonance (NMR) structure and having α-helix, 4-fold β-sheet, and hydrophobic core features, is used as a model protein to study protein soil mineral interactions and gain insights on structural changes and potential degradation of protein. From our simulations, we observe little change to the hydrated Gb1 structure over the kaolinite, montmorillonite, and goethite surfaces relative to its solvated structure without these mineral surfaces present. Over the Na⁺ -birnessite basal surface, however, the Gb1 structure is highly disturbed as a result of interaction with this birnessite surface. Unraveling of the Gb1 β-sheet at specific turns and a partial unraveling of the α-helix is observed over birnessite, which suggests specific vulnerable residue sites for oxidation or hydrolysis possibly leading to fragmentation

Geochemical Characterization of Chromate Contamination in the 100 Area Vadose Zone at the Hanford Site

The major objectives of the proposed study were to: 1.) determine the leaching characteristics of hexavalent chromium [Cr(VI)] from contaminated sediments collected from 100 Area spill sites; 2.) elucidate possible Cr(VI) mineral and/or chemical associations that may be responsible for Cr(VI) retention in the Hanford Site 100 Areas through the use of i.) macroscopic leaching studies and ii.) microscale characterization of contaminated sediments; and 3.) provide information to construct a conceptual model of Cr(VI) geochemistry in the Hanford 100 Area vadose zone. In addressing these objectives, additional benefits accrued were: (1) a fuller understanding of Cr(VI) entrained in the vadose zone that will that can be utilized in modeling potential Cr(VI) source terms, and (2) accelerating the Columbia River 100 Area corridor cleanup by providing valuable information to develop remedial action based on a fundamental understanding of Cr(VI) vadose zone geochemistry. A series of macroscopic column experiments were conducted with contaminated and uncontaminated sediments to study Cr(VI) desorption patterns in aged and freshly contaminated sediments, evaluate the transport characteristics of dichromate liquid retrieved from old pipelines of the 100 Area; and estimate the effect of strongly reducing liquid on the reduction and transport of Cr(VI). Column experiments used the < 2 mm fraction of the sediment samples and simulated Hanford groundwater solution. Periodic stop-flow events were applied to evaluate the change in elemental concentration during time periods of no flow and greater fluid residence time. The results were fit using a two-site, one dimensional reactive transport model. Sediments were characterized for the spatial and mineralogical associations of the contamination using an array of microscale techniques such as XRD, SEM, EDS, XPS, XMP, and XANES. The following are important conclusions and implications. Results from column experiments indicated that most of contaminant Cr travels fast through the sediments and appears as Cr(VI) in the effluents. The significance of this for groundwater concentrations would, however, depend on the mass flux of recharge to the water table. adsorption of Cr(VI) to sediments from spiked Cr(VI) solution is low; calculated retardation coefficients are close to one. Calcium polysulfide solutions readily reduced Cr(VI) to Cr(III) in column experiments. However a significant amount of the Cr(VI) was mobilized ahead of the polysulfide solution front. This has significant implications for in-situ reductive remediation techniques. The experiments suggest that it would be difficult to design a remedial measure using infiltration of liquid phase reductants without increasing transport of Cr(VI) toward the water table. The microscopic characterization results are consistent with the column studies. Cr(VI) is found as ubiquitous coatings on sediment grain surfaces. Small, higher concentration, chromium sites are associated with secondary clay mineral inclusions, with occasional barium chromate minerals, and reduced to Cr(III) in association with iron oxides that are most likely magnetite primary minerals. Within the restricted access domains of sediment matrix, ferrous iron could also diffuse from in situ, high-surface-area minerals to cause the reductive immobilization of chromate. This process may be favored at microscale geochemical zones where ferrous iron could be supplied. Once nucleated, micrometer-scale precipitates are favored as growing locales for further accumulation, causing the formation of discrete zones of Cr(III)

Single Pass Flow-Through (SPFT) Test Results of Fluidized Bed Steam Reforming (FBSR) Waste Forms used for LAW Immobilization-#12252

ABSTRACT Several supplemental technologies for treating and immobilizing Hanford low activity waste (LAW) are being evaluated. One such immobilization technology being considered is the Fluidized Bed Steam Reforming (FBSR) product, which is granular and will be monolithed into a final waste form. The granular component is composed of insoluble sodium aluminosilicate (NAS) feldspathoid minerals. Production of the FBSR mineral product has been demonstrated at the industrial, engineering, and laboratory scales. Single-Pass Flow-Through (SPFT) tests at various flow rates have been conducted with the granular products fabricated using the engineering-and laboratory-scale methods. Results show that the forward dissolution rate for the engineering-scale mineral product is 0.6 (±0.2)×10 -3 g/m 2 d while the forward dissolution rate for the laboratory-scale mineral product is 1.3 (±0.5)×10 -3 g/m 2 d

Getters for improved technetium containment in cementitious waste forms.

A cementitious waste form, Cast Stone, is a possible candidate technology for the immobilization of low activity nuclear waste (LAW) at the Hanford site. This work focuses on the addition of getter materials to Cast Stone that can sequester Tc from the LAW, and in turn, lower Tc release from the Cast Stone. Two getters which produce different products upon sequestering Tc from LAW were tested: Sn(II) apatite (Sn-A) that removes Tc as a Tc(IV)-oxide and potassium metal sulfide (KMS-2) that removes Tc as a Tc(IV)-sulfide species, allowing for a comparison of stability of the form of Tc upon entering the waste form. The Cast Stone with KMS-2 getter had the best performance with addition equivalent to ∼0.08wt% of the total waste form mass. The observed diffusion (Dobs) of Tc decreased from 4.6±0.2×10-12cm2/s for Cast Stone that did not contain a getter to 5.4±0.4×10-13cm2/s for KMS-2 containing Cast Stone. It was found that Tc-sulfide species are more stable against re-oxidation within getter containing Cast Stone compared with Tc-oxide and is the origin of the decrease in Tc Dobs when using the KMS-2