Kemod: A Mixed Chemical Kinetic And Equilibrium Model of Aqueous and Solid Phase Geochemical Reactions

This report presents the development of a mixed chemical Kinetic and Equilibrium MODel (KEMOD), in which every chemical species can be treated either as a equilibrium-controlled or as a kinetically controlled reaction. The reaction processes include aqueous complexation, adsorption/ desorption, ion exchange, precipitation/dissolution, oxidation/reduction, and acid/base reactions. Further development and modification of KEMOD can be made in: (1) inclusion of species switching solution algorithms, (2) incorporation of the effect of temperature and pressure on equilibrium and rate constants, and (3) extension to high ionic strength

Remediation of Uranium in the Hanford Vadose Zone Using Ammonia Gas: FY 2010 Laboratory-Scale Experiments

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

Hanford 100N Area Apatite Emplacement: Laboratory Results of Ca-Citrate-PO4 Solution Injection and Sr-90 Immobilization in 100N Sediments

This report summarizes laboratory scale studies investigating the remediation of Sr-90 by Ca-citrate-PO4 solution injection/infiltration to support field injection activities in the Hanford 100N area. This study is focused on experimentally testing whether this remediation technology can be effective under field scale conditions to mitigate Sr-90 migration 100N area sediments into the Columbia River. Sr-90 is found primarily adsorbed to sediments by ion exchange (99% adsorbed, < 1% in groundwater) in the upper portion of the unconfined aquifer and lower vadose zone. Although primarily adsorbed, Sr-90 is still considered a high mobility risk as it is mobilized by seasonal river stage increases and by plumes of higher ionic strength relative to groundwater. This remediation technology relies upon the Ca-citrate-PO4 solution forming apatite precipitate [Ca6(PO4)10(OH)2], which incorporates some Sr-90 during initial precipitation and additionally slowly incorporates Sr-90 by solid phase substitution for Ca. Sr substitution occurs because Sr-apatite is thermodynamically more stable than Ca-apatite. Once the Sr-90 is in the apatite structure, Sr-90 will decay to Y-90 (29.1 y half-life) then Zr-90 (64.1 h half-life) without the potential for migration into the Columbia River. For this technology to be effective, sufficient apatite needs to be emplaced in sediments to incorporate Sr and Sr-90 for 300 years (~10 half-lives of Sr-90), and the rate of incorporation needs to exceed the natural groundwater flux rate of Sr in the 100N area. A primary objective of this study is to supply an injection sequence to deliver sufficient apatite into subsurface sediments that minimizes initial mobility of Sr-90, which occurs because the injection solution has a higher ionic strength compared to groundwater. This can be accomplished by sequential injections of low, then high concentration injection of Ca-citrate-PO4 solutions. Assessment of low concentration Ca-citrate-PO4, citrate-PO4, and PO4 solutions show greater Sr and Sr-90 incorporation during initial precipitation and less initial mobilization with solutions with low Ca2+ concentration. While all solutions showed nearly the same Sr uptake into apatite (14 to 17% by 2 weeks, 21% to 30% by 5 weeks), the incorporation efficiency (i.e., mM Sr incorporated per mM PO4 injected) was higher for solutions containing citrate. The Sr incorporation rate into apatite during initial precipitation (by 1 month) averaged 4.64 ± 1.9 x 10-4 h-1 (half-life 1500 ± 430 h, 8.85 x 10-7 mg Sr/day/mg apatite). The injection solution used in field injections #3 to #18 (10 mM PO4, 1 mM Ca, 2.5 mM citrate), which is deficient in Ca (a total of 16.7 mM needed to form apatite with 10 mM of PO4), resulted in the initial Sr and Ca peak (24 h) at 4.7x groundwater. By 30 days, the aqueous Sr concentration was 0.28x groundwater and Ca 0.43x groundwater, as both Sr and Ca are used to form initial apatite precipitates. Reactive transport simulation of the complex ion exchange, biodegradation, and precipitation processes showed that the initial Sr groundwater increase mobilized only 1.5% of the Sr mass in sediments. Citrate biodegradation, a necessary step in Ca-citrate-PO4 solutions forming apatite, had an average half-life of 50 h (at aquifer sediment/water ratio and temperature), and decreased an order of magnitude with sediment depth as the microbial biomass decreased five orders of magnitude. The rate of citrate biodegradation was relatively invariant with biomass and water saturation (50% to 100%, for vadose zone infiltration) possibly due to significant microbial injection using river water and subsurface microbial mobilization

Interim Report: 100-NR-2 Apatite Treatability Test: Low Concentration Calcium Citrate-Phosphate Solution Injection for In Situ Strontium-90 Immobilization

Following an evaluation of potential Sr-90 treatment technologies and their applicability under 100-NR-2 hydrogeologic conditions, U.S. Department of Energy, Fluor Hanford, Inc., Pacific Northwest National Laboratory, and the Washington Department of Ecology agreed that the long-term strategy for groundwater remediation at 100-N Area will include apatite sequestration as the primary treatment, followed by a secondary treatment if necessary (most likely phytoremediation). Since then, the agencies have worked together to agree on which apatite sequestration technology has the greatest chance of reducing Sr-90 flux to the river at a reasonable cost. In July 2005, aqueous injection, (i.e., the introduction of apatite-forming chemicals into the subsurface) was endorsed as the interim remedy and selected for field testing. Studies are in progress to assess the efficacy of in situ apatite formation by aqueous solution injection to address both the vadose zone and the shallow aquifer along the 300 ft of shoreline where Sr-90 concentrations are highest. This report describes the field testing of the shallow aquifer treatment

Use of the generalized integral transform method for solving equations of solute transport in porous media

The generalized integral transform technique (GITT) is applied to solve the one-dimensional advection-dispersion equation (ADE) in heterogeneous porous media coupled with either linear or nonlinear sorption and decay. When both sorption and decay are linear, analytical solutions are obtained using the GITT for one-dimensional ADEs with spatially and temporally variable flow and dispersion coefficient and arbitrary initial and boundary conditions. When either sorption or decay is nonlinear the solutions to ADEs with the GITT are hybrid analytical-numerical. In both linear and nonlinear cases, the forward and inverse integral transforms for the problems described in the paper are apparent and straightforward. Some illustrative examples with linear sorption and decay are presented to demonstrate the application and check the accuracy of the derived analytical solutions. The derived hybrid analytical-numerical solutions are checked against a numerical approach and demonstratively applied to a nonlinear transport example, which simulates a simplified system of iron oxide bioreduction with nonlinear sorption and nonlinear reaction kinetics

Foam-Delivery of Remedial Amendments for Enhanced Vadose Zone Metals and Radionuclides Remediation -9465

ABSTRACT The remediation of metals and radionulides contamination, such as Cr(VI), Tc-99, and Sr-90 in the U.S. DOE Hanford Site vadose zone is a critical need. Water-based remedial amendments delivery to the deep vadose zone is facing significant technical challenges. Water-based delivery will easily leach out the highly mobile pollutants therefore contaminate the underlying aquifer. Preferential flow of the amendment-laden solution in the vadose zone due to the formation heterogeneity is difficult to overcome, resulting in bypassing of the less permeable zones. Foam has unique transport properties in the vadose zone that enable mitigation on the mobilization of mobile contaminants and enhance the sweeping over heterogeneous systems. Calcium polysulfide (CPS) is a remedial amendment that can be used to reduce and immobilize hexavalent chromium [Cr(VI)] and other redox-sensitive radionuclides/metals in the vadose zone. The delivery of CPS to the vadose zone using foam and the immobilization of Cr(VI) via reduction by the foam-delivered CPS was investigated in this study. Batch tests were conducted to select the foam-generating CPS-surfactant solutions, to determine the solution foamability and the reducing potential of CPS-containing foams, and to study the influence of foam quality, surfactant concentration, and CPS concentration on foam stability. Column experiments were performed to test the foam delivery of CPS to sediments under conditions similar to field vadose zone, to study the foam transport and interaction with sediments, and to determine the extent of Cr(VI) immobilization using this novel delivery approach. CPS-containing foams with high reducing potential were prepared based on the batch tests. Sediment reduction by foam-delivered CPS was observed in the column studies. Significant mobilization of Cr(VI) from sediments occurred when CPS was delivered in aqueous solution. The Cr(VI) mobilization was minimized when CPS was delivered by foams, resulting in significant Cr(VI) in-situ immobilization. Foam delivery of citrate-phosphate mixture to vadose zone sediments for apatite precipitation was also tested in preliminary column and 2-D flow cell tests. The results of this study demonstrated for the first time that foam injection can be successfully used for CPS delivery and that foam-delivered CPS can be applied for Cr(VI) immobilization in contaminated vadose zones. A second solution (Ca-citrate-PO 4 ) was also foam-delivered into vadose zone sediments. This sediment will result in precipitation of apatite, which then adsorbs and incorporates Sr (and Sr-90) into the structure. 1-D and 2-D foam injection experiments resulted in a wide area of apatite precipitate