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

Technical Basis for Gas-Phase Vadose Zone Remediation Technologies at Hanford: A Review -12186

ABSTRACT In situ vadose zone remediation approaches are being evaluated as potential options to mitigate the transport of inorganic and radionuclide contaminants from the vadose zone to the groundwater. Some of the candidate approaches are based on changing the contaminant or subsurface conditions in a way that slows downward migration of the contaminants through the vadose zone using amendments delivered in the gas-phase. Two promising approaches that have undergone testing at Hanford include soil desiccation to address technetium-99 contamination and ammonia-induced sequestration of uranium. For soil desiccation, a dry gas is injected to desiccate a targeted portion of the subsurface and thereby decrease contaminant movement by removing moisture and decreasing the hydraulic conductivity of the desiccated zone. Ammonia-induced sequestration of uranium relies on changing the pore water chemistry, primarily through pH changes, to induce dissolution and precipitation processes that decrease the amount of mobile uranium in the vadose zone

Abiotic reduction of aquifer materials by dithionite: A promising in-situ remediation technology

Laboratory batch and column experiments were conducted with Hanford sediments to develop the capability to predict (1) the longevity of dithionite in these systems, (2) its efficiency as a reductant of structural iron, and (3) the longevity and reactivity of the reduced iron with soluble inorganic and organic species. After an initial induction period, the loss of dithionite by disproportionation and oxidation could be described by pseudo-first-order (PFO) kinetics. Other than the initial reaction with ferric iron, the primary factor promoting loss of dithionite in this system was disproportion nation via heterogeneous catalysis at mineral surfaces. The efficiency of the reduction of structural iron was nearly 100% for the first fourth of the ferric iron, but declined exponentially with higher degrees of reduction so that 75% of the ferric iron could be reduced. This decrease in reduction efficiency probably was related to differences in the accessibility of ferric iron in the mineral particles, with iron in clay-sized particles being the most accessible and that in silt- and sand-sized particles less accessible. Flow-through column studies showed that a reduced-sediment barrier created in this manner could maintain a reducing environment

Feasibility of In Situ Redox Manipulation of Subsurface Sediments for RDX Remediation at Pantex

This laboratory study was conducted to assess RDX (hexahydro-1,3,5-trinitro-1,3,5 triazine) abiotic degradation by chemically reduced sediments and other geochemical aspects of the application of this technology to remediation of RDX contamination in groundwater at the U.S. DOE Pantex facility..

In Situ Redox Manipulation Proof-of-Principle Test at the Fort Lewis Logistics Center: Final Report

Pacific Northwest National Laboratory (PNNL) conducted a proof-of-principle test at the Fort Lewis Logistics Center to determine the feasibility of using the In Situ Redox Manipulation (ISRM) technology for remediating groundwater contaminated with dissolved trichloroethylene (TCE). ISRM creates a permeable treatment zone in the subsurface to remediate redox-sensitive contaminants in groundwater. The permeable treatment zone is formed by injecting a chemical reducing agent (sodium dithionite with pH buffers) into the aquifer through a well to reduce the naturally occurring ferric iron in the sediments to ferrous iron. Once the reducing agent is injected and given sufficient time to react with aquifer sediments, residual chemicals and reaction products are withdrawn from the aquifer through the same well used for the injection. Redox-sensitive contaminants such as TCE, moving through the treatment zone under natural groundwater flow conditions, are destroyed. TCE is degraded via reductive dechlorination within the ISRM treatment zone to benign degradation products (i.e., acetylene, ethylene). Prior to the proof-of-principle field test, the ISRM technology was successfully demonstrated in laboratory experiments for the reductive dechlorination of dissolved TCE using sediments from the Fort Lewis site. The Logistics Center was placed on the National Priorities List in December 1989 because of TCE contamination in groundwater beneath the site. A Federal Facilities Agreement between the Army, the U.S. Environmental Protection Agency, and the Washington State Department of Ecology became effective in January 1990, and a Record of Decision (ROD) was signed in September 1990. The major components of the ROD included installation of two pump-and-treat systems for the upper aquifer and further investigation of the lower aquifer and other potential sources of contamination. The pump-and-treat systems became operational in August 1995. Fort Lewis asked PNNL to provide technical support in accelerating Installation Restoration Program site remediation and significantly reducing site life-cycle costs at the Logistics Center. In support of this program, ISRM was selected as an innovative technology for bench and field-scale demonstration. Emplacement of the ISRM treatment zone was accomplished through a series of four separate dithionite injection tests conducted between November 10, 1998 and March 29,2000. An extensive program of chemical monitoring was also performed before, during, and after each injection to evaluate the performance of ISRM. Prior to emplacement of the ISRM treatment zone, the site was extensively characterized with respect to geologic, hydrologic, and geochemical properties. Sediment core samples collected for the characterization studies were analyzed in bench-scale column tests at PNNL to determine reducible iron content. These site-specific hydrogeologic and geochemical data were used to develop the emplacement design of the pilot-scale (i.e., single injection well) ISRM treatment zone. Performance data obtained from the proof-of-principle test indicate that field-scale reductive dechlorination of TCE using the ISRM technology is feasible. A treatment zone was created in the subsurface that reduced TCE concentrations as much as 92% on the downgradient side of the reduced zone, from a background concentration of approximately 140 ppb to approximately 11 ppb. The appearance of the principal degradation product, acetylene, also confirmed that TCE destruction was occurring. Analysis of sediment samples collected from post-test boreholes showed a high degree of iron reduction, which helped to confirm the effectiveness of the treatment zone emplacement. Another important goal of the testing program was to provide assurances that chemical treatment of the subsurface did not result in undesirable secondary effects, including formation of toxic TCE degradation products, mobilization of trace elements, and degradation of hydraulic performance. Results obtained from the Fort Lewis ISRM proof-of-principle test, which are consistent with results from previous ISRM studies (both bench- and field-scale), indicate that no significant secondary effects were identified that could limit full-scale application of this technology

Desorption Behavior of Trichloroethene and Tetrachloroethene in u.s. Department of Energy Savannah River Site Unconfined Aquifer Sediments

Sorption is governed by the physico-chemical processes that partition solutes between the aqueous and solid phases in aquifers. For environmental systems, a linear equilibrium relationship between the amount of contaminant in the alternative phases is often assumed. In this traditional approach, the distribution coefficient, or K{sub d}, is a ratio of contaminant associated with the solid phase to the contaminant in the water phase. Recent scientific literature has documented time-dependant behaviors in which more contaminant mass is held in the solid phase than predicted by the standard model. Depending on the specific conceptualization, this has been referred to as nonlinear sorption, time-variable sorption, or ''irreversible sorption''. The potential impact of time-variable sorption may be beneficial or detrimental depending on the specific conditions and remediation goals. Researchers at the Pacific Northwest National Laboratory (PNNL) have been studying this process to evaluate how various soil types will affect this process for sites contaminated with chlorinated solvents. The results described in this report evaluate sorption-desorption of trichloroethylene (TCE) and tetrachloroethylene (PCE) in Savannah River Site (SRS) soils. The results of this study will be combined with ongoing PNNL research to provide a more comprehensive look at this process and its impact on contaminant plume stability and sustainability. Importantly, while the results of the study documented differences in sorption properties between two tested SRS soils, the data indicated that ''irreversible sorption'' is not influencing the sorption-desorption behaviors of TCE and PCE for these soils

Treatability Study of In Situ Technologies for Remediation of Hexavalent Chromium in Groundwater at the Puchack Well Field Superfund Site, New Jersey

This treatability study was conducted by Pacific Northwest National Laboratory (PNNL), at the request of the U. S. Environmental Protection Agency (EPA) Region 2, to evaluate the feasibility of using in situ treatment technologies for chromate reduction and immobilization at the Puchack Well Field Superfund Site in Pennsauken Township, New Jersey. In addition to in situ reductive treatments, which included the evaluation of both abiotic and biotic reduction of Puchack aquifer sediments, natural attenuation mechanisms were evaluated (i.e., chromate adsorption and reduction). Chromate exhibited typical anionic adsorption behavior, with greater adsorption at lower pH, at lower chromate concentration, and at lower concentrations of other competing anions. In particular, sulfate (at 50 mg/L) suppressed chromate adsorption by up to 50%. Chromate adsorption was not influenced by inorganic colloids

Effect of Geochemical and Physical Heterogeneity on the Hanford 100D Area In Situ Redox Manipulation Barrier Longevity

The purpose of this study was to quantify the influence of physical and/or geochemical heterogeneities in the Hanford 100D area In Situ Redox Manipulation (ISRM) barrier, which may be contributing to the discontinuous chromate breakthrough locations along the 65-well (2,300 ft long) barrier. Possible causes of chromate breakthrough that were investigated during this study include: (1) high hydraulic conductivity zones; (2) zones of low reducible iron; and (3) high hydraulic conductivity zones with low reducible iron. This laboratory-scale investigation utilized geochemical and physical characterization data collected on 0.5 to 1 foot intervals from four borehole locations. Results of this laboratory study did not provide definitive support any of the proposed hypotheses for explaining chromate breakthrough at the Hanford 100-D Area ISRM barrier. While site characterization data indicate a significant degree of vertical variability in both physical and geochemical properties in the four boreholes investigated, lateral continuity of high conductivity/low reductive capacity zones was not observed. The one exception was at the water table, where low reductive capacity and high-K zones were observed in 3 of four boreholes. Laterally continuous high permeability zones that contain oxic sediment near the water table is the most likely explanation for high concentration chromium breakthrough responses observed at various locations along the barrier. A mechanism that could explain partial chromate breakthrough in the ISRM barrier is the relationship between the field reductive capacity and the rate of chromate oxidation. Subsurface zones with low reductive capacity still have sufficient ferrous iron mass to reduce considerable chromate, but the rate of chromate reduction slows by 1 to 2 orders of magnitude relative to sediments with moderate to high reductive capacity. The original barrier longevity estimate of 160 pore volumes for homogeneous reduced sediment, or approximately 20 years, (with 5 mg/L dissolved oxygen and 2 ppm chromate) is reduced to 85 pore volumes (10 years) when the wide spread 60 ppm nitrate plume is included in the calculation. However, this reduction in barrier lifetime is not as great for high permeability channels, as there is insufficient time to reduce nitrate (and consume ferrous iron). If the cause of laterally discontinuous breakthrough of chromate along the ISRM barrier is due to oxic transport of chromate near the water table, additional dithionite treatment in these zones will not be effective. Treatment near the water table with a technology that emplaces considerable reductive capacity is needed, such as injectable zero valent iron

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