[en] In this study 233Uranyl nitrate was added to uranium (U) contaminated Hanford 300 Area sediment and incubated under moist conditions for 1 year. It hypothesized that geochemical transformations and/or physical processes will result in decreased extractability of 233U as the incubation period increases, and eventually the extraction behavior of the 233U spike will be congruent to contaminant U that has been associated with sediment for decades. Following 1 week, 1 month, and 1 year incubation periods, sediment extractions were performed using either batch or dynamic (sediment column flow) chemical extraction techniques. Overall, extraction of U from sediment using batch extraction was less complicated to conduct compared to dynamic extraction, but dynamic extraction could distinguish the range of U forms associated with sediment which are eluted at different times.

[en] This laboratory-scale investigation is focused on decreasing mobility of uranium in subsurface contaminated sediments in the vadose zone by in situ geochemical manipulation at low water content. This geochemical manipulation of the sediment surface phases included reduction, pH change (acidic and alkaline), and additions of chemicals (phosphate, ferric iron) to form specific precipitates. Reactants were advected into 1-D columns packed with Hanford 200 area U-contaminated sediment as a reactive gas (for CO2, NH3, H2S, SO2), with a 0.1% water content mist (for NaOH, Fe(III), HCl, PO4) and with a 1% water content foam (for PO4). Because uranium is present in the sediment in multiple phases, changes in U surface phases were evaluated with a series of liquid extractions that dissolve progressively less soluble phases and electron microbe identification of mineral phases. In terms of the short-term decrease in U mobility (in decreasing order), NH3, NaOH mist, CO2, HCl mist, and Fe(III) mist showed 20% to 35% change in U surface phases. The two reductive gas treatments (H2S and SO2) showed little change. For long-term decrease in U transport, mineral phases created that had low solubility (phosphates, silicates) were desired, so NH3, phosphates (mist and foam delivered), and NaOH mist showed the greatest formation of these minerals.

[en] Aluminum-rich, hyperalkaline (pH > 13.5) and saline high-level nuclear waste (HLW) fluids at elevated temperatures (>50 deg C), that possibly contained as much as 0.41 mol L^-1Cr(VI), accidentally leaked to the sediments at the Hanford Site, WA. These extreme conditions promote base-induced dissolution of soil minerals which may affect Cr(VI)_aq mobility. Our objective was to investigate Cr(VI)_aq transport in sediments leached with HLW simulants at 50 deg C, under CO₂ and O₂ free conditions. Results demonstrated that Cr(VI)_aq fate was closely related to dissolution, and Cr(VI)_aq mass loss was negligible in the first pore volumes but increased significantly thereafter. Similar to dissolution, Cr(VI)_aq attenuation increased with increasing fluid residence time and NaOH concentration but decreased with Al concentrations in the leaching solutions. Aqueous Cr(VI) removal rate half-lives varied from 1.2 to 230 h with the fastest at the highest base concentration, lowest Al concentration, greatest reaction time, and lowest Cr(VI) concentration in the leaching solution. The rate of Cr(VI) removal (normalized to 1 kg of solution) varied from 0.83 x 10^-9 (+-0.44 x 10^-9) to 9.16 x 10^-9(+-1.10 x 10^-9) mol s^-1. The predominant mechanism responsible for removing Cr(VI) from the aqueous phase appears to be homogeneous Cr(VI) reduction to Cr(III) by Fe(II) released during mineral dissolution. Cr(VI)_aq removal was time-limited probably because it was controlled by the rate of Fe(II) release into the soil solution upon mineral dissolution, which was also a time-limited process, and other processes that may act to lower Fe(II)_aq activity

[en] This laboratory-scale investigation is focused on decreasing mobility of uranium in subsurface contaminated sediments in the vadose zone by in situ geochemical manipulation at low water content. This geochemical manipulation of the sediment surface phases included reduction, pH change (acidic and alkaline), and additions of chemicals (phosphate, ferric iron) to form specific precipitates. Reactants were advected into 1-D columns packed with Hanford 200 area U-contaminated sediment as a reactive gas (for CO2, NH3, H2S, SO2), with a 0.1% water content mist (for NaOH, Fe(III), HCl, PO4) and with a 1% water content foam (for PO4). Uranium is present in the sediment in multiple phases that include (in decreasing mobility): aqueous U(VI) complexes, adsorbed U, reduced U(IV) precipitates, rind-carbonates, total carbonates, oxides, silicates, phosphates, and in vanadate minerals. Geochemical changes were evaluated in the ability to change the mixture of surface U phases to less mobile forms, as defined by a series of liquid extractions that dissolve progressively less soluble phases. Although liquid extractions provide some useful information as to the generalized uranium surface phases (and are considered operational definitions of extracted phases), positive identification (by x-ray diffraction, electron microprobe, other techniques) was also used to positively identify U phases and effects of treatment. Some of the changes in U mobility directly involve U phases, whereas other changes result in precipitate coatings on U surface phases. The long-term implication of the U surface phase changes to alter U mass mobility in the vadose zone was then investigated using simulations of 1-D infiltration and downward migration of six U phases to the water table. In terms of the short-term decrease in U mobility (in decreasing order), NH3, NaOH mist, CO2, HCl mist, and Fe(III) mist showed 20% to 35% change in U surface phases. Phosphate addition (mist or foam advected) showed inconsistent change in aqueous and adsorbed U, but significant coating (likely phosphates) on U-carbonates. The two reductive gas treatments (H2S and SO2) showed little change. For long-term decrease in U reduction, mineral phases created that had low solubility (phosphates, silicates) were desired, so NH3, phosphates (mist and foam delivered), and NaOH mist showed the greatest formation of these minerals. In addition, simulations showed the greatest decrease in U mass transport time to reach groundwater (and concentration) for these silicate/phosphate minerals. Advection of reactive gasses was the easiest to implement at the laboratory scale (and presumably field scale). Both mist and foam advection show promise and need further development, but current implementation move reactants shorter distances relative to reactive gasses. Overall, the ammonia and carbon dioxide gas had the greatest overall geochemical performance and ability to implement at field scale. Corresponding mist-delivered technologies (NaOH mist for ammonia and HCl mist for carbon dioxide) performed as well or better geochemically, but are not as easily upscaled. Phosphate delivery by mist was rated slightly higher than by foam delivery simply due to the complexity of foam injection and unknown effect of U mobility by the presence of the surfactant.

[en] Harmful contaminants such as Cr(VI) and TCE can be removed from groundwater by reactions with chemically reduced subsurface sediments. This paper studies the optimal selection of the number of wells, the injection rate, and the number of regenerations of a large-scale Fe(II) barrier for Cr(VI) remediation at Hanford, WA. The process model consists of two parts: (a) the creation of the Fe(II) barrier by the injection of a dithionite reagent and (b) the reoxidation of the barrier by Cr(VI) and oxygen in the invading groundwater. The solution to the process model is used to develop the total cost as a function of the design variables. This cost model is applied to the Cr(VI) contamination at Hanford to obtain the optimal design configuration and its sensitivity to cost and process uncertainties

[en] Sr-90 present in groundwater and the vadose zone at the Hanford 100N area due to past waste disposal practices has reached the nearby Columbia River, as evidenced by Sr-90 concentrations in near river wells and aquifer tubes and near shore sediments. Sr-90 is currently being remediated by adsorption onto apatite (55 times stronger than Sr-90 adsorption to sediment), followed by incorporation of the Sr-90 into the apatite structure. If the Sr-90 can remain immobilized for 300 years (∼ten 29.1-yr half-lives of Sr-90 decay), it will have decayed below regulatory limits to Y-90 and to stable Zr-90. Apatite (Ca10(PO4)6(OH)2) is being precipitated in situ in saturated zone sediments by injection of a aqueous solution of Ca-citrate and Na-phosphate through a series of 16 wells. For the treatability study, field scale demonstration of the technology was implemented through injection of a low-concentration, apatite-forming solution, followed by high concentration solution injections as required to emplace sufficient treatment capacity to meet treatability test objectives. Analysis of field cores collected after the low concentration injections indicates that targeted apatite contents were achieved and that ∼25% of the Sr-90 associated with the sediment was incorporated in the apatite structure. Aqueous Sr-90 monitoring in four compliance monitoring wells over a year following the high concentration injections indicates 84% to 95% decrease in Sr-90 concentrations (relative to the low and high end of the baseline range, respectively). Cores are currently being analyzed to confirm the apatite mass and Sr-90 substitution in apatite after these high concentration injections.

[en] A research tool for modeling the reactive flow and transport of groundwater contaminants in multiple dimensions is presented. Arbitrarily complex coupled kinetic-equilibrium heterogeneous reaction networks, automatic code generation, transfer-function based solutions, parameter estimation, high-resolution methods for advection, and robust solvers for the mixed kinetic-equilibrium chemistry are some of the features of reactive flow and transport (RAFT) that make it a versatile research tool in the modeling of a wide variety of laboratory and field experiments. The treatment of reactions is quite general so that RAFT can be used to model biological, adsorption/desorption, complexation, and mineral dissolution/precipitation reactions among others. The integrated framework involving automated code generation and parameter estimation allows for the development, characterization, and evaluation of mechanistic process models. The model is described and used to solve a problem in competitive adsorption that illustrates some of these features. The model is also used to study the development of an in situ Fe(II)-zone by encouraging the growth of an iron-reducing bacterium with lactate as the electron donor. Such redox barriers are effective in sequestering groundwater contaminants such as chromate and TCE

[en] Research proposals were submitted to the Scientific and Technical Basis for In Situ Treatment of Metals and Radionuclides Technical Working Group under the US Department of Energy (DOE) Environmental Management Office (specifically, EM-22). After a peer review and selection process, the proposal, 'Foam Delivery of Remedial Amendments to Deep Vadose Zone for Metals and Radionuclides Remediation,' submitted by Pacific Northwest National Laboratory (PNNL) was selected for support by the program. A research plan was requested for this EM funded project. The overall objective of this project is to develop foam delivery technology for the distribution of remedial amendments to deep vadose zone sediments for in situ immobilization of metal and radionuclide contaminants. The focus of this research in FY 2009 is on the physical aspects of the foam delivery approach. Specific objectives are to (1) study the foam quality (i.e. the gas volume fraction in foam) influence on injection pressure, (2) study the sediment air permeability influence on injection pressure, (3) investigate liquid uptake in sediment and determine whether a water front will be formed during foam delivery, (4) test amendment distance (and mass) delivery by foam from the injection point, (5) study the enhanced sweeping over heterogeneous systems (i.e., low K zones) by foam delivery relative to water-based delivery under vadose zone conditions, and (6) numerically simulate foam delivery processes in the vadose zone. Laboratory scale experiments will be conducted at PNNL to study a range of basic physical aspects of the foam propagation in sediments, including foam quality and sediment permeability influence on injection pressure, liquid uptake, and foam sweeping across heterogeneous systems. This study will be augmented with separate studies to be conducted at MSE Technology Applications, Inc. (MSE) to evaluate foam transport and amendment delivery at the intermediate-scale. The results of intermediate-scale tests will be used to bridge the gap between the small-scale foam transport studies and the field-scale demonstration. Numerical simulation studies on foam delivery under vadose conditions will be performed to simulate observed foam transport behavior under vadose zone conditions and predict the foam delivery performance at field-scale

[en] This investigation is focused on refining an in situ technology for vadose zone remediation of uranium by the addition of ammonia (NH3) gas. Objectives are to: (a) refine the technique of ammonia gas treatment of low water content sediments to minimize uranium mobility by changing uranium surface phases (or coat surface phases), (b) identify the geochemical changes in uranium surface phases during ammonia gas treatment, (c) identify broader geochemical changes that occur in sediment during ammonia gas treatment, and (d) predict and test injection of ammonia gas for intermediate-scale systems to identify process interactions that occur at a larger scale and could impact field scale implementation. Overall, NH3 gas treatment of low-water content sediments appears quite effective at decreasing aqueous, adsorbed uranium concentrations. The NH3 gas treatment is also fairly effective for decreasing the mobility of U-carbonate coprecipitates, but shows mixed success for U present in Na-boltwoodite. There are some changes in U-carbonate surface phases that were identified by surface phase analysis, but no changes observed for Na-boltwoodite. It is likely that dissolution of sediment minerals (predominantly montmorillonite, muscovite, kaolinite) under the alkaline conditions created and subsequent precipitation as the pH returns to natural conditions coat some of the uranium surface phases, although a greater understanding of these processes is needed to predict the long term impact on uranium mobility. Injection of NH3 gas into sediments at low water content (1% to 16% water content) can effectively treat a large area without water addition, so there is little uranium mobilization (i.e., transport over cm or larger scale) during the injection phase.

[en] Solid-phase interactions and speciation are important to radioiodine transport in groundwater. At the Hanford Site in Southeastern Washington State, iodate (IO₃⁻) is the main aqueous species in dilute radioiodine groundwater plumes. Like other oxyanions, IO₃⁻ may be incorporated into and/or adsorbed onto calcite, a common mineral at Hanford, decreasing its mobility in the environment. A series of macroscale batch experiments combined with solid-phase characterization were conducted to identify variables impacting time-dependent aqueous IO₃⁻ removal via calcite precipitation and determine the location of IO₃⁻ within the calcite crystal structure. Results demonstrated 11.5–97% aqueous IO₃⁻ removal during initial rapid calcite precipitation. Incorporation was apparently the main removal mechanism, although later slower precipitation and/or adsorption may have also contributed to IO₃⁻ removal. Using a higher concentration of the calcite-forming solutions (i.e., using 1 M vs. 0.1 M concentrations) resulted in an increase in the amount of precipitated calcite and a greater percentage of IO₃⁻ removed; however, calcite formed with lower molarity solutions resulted in higher IO₃⁻ mass (µg/g) removal. Solubility testing of laboratory-produced calcites showed only small differences in solubility for calcite with and without IO₃⁻ incorporated into the structure. Evidence collected from SEM/FIB and TEM/SAED suggested that the IO₃⁻ incorporated into calcite was present in regions close to the surface (implying potential easy release upon calcite dissolution).