Use of Polyphosphate to Decrease Uranium Leaching in Hanford 300 Area Smear Zone Sediments

The primary objective of this study is to summarize the laboratory investigations performed to evaluate short- and long-term effects of phosphate treatment on uranium leaching from 300 area smear zone sediments. Column studies were used to compare uranium leaching in phosphate-treated to untreated sediments over a year with multiple stop flow events to evaluate longevity of the uranium leaching rate and mass. A secondary objective was to compare polyphosphate injection, polyphosphate/xanthan injection, and polyphosphate infiltration technologies that deliver phosphate to sediment

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..

100-NR-2 Apatite Treatability Test: An update on Barrier Performance

This report updates a previous report covering the performance of a permeable reactive barrier installed at 100N. In this report we re-evaluate the results after having an additional year of performance monitoring data to incorporate

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

Following an evaluation of potential strontium-90 (90Sr) treatment technologies and their applicability under 100-NR-2 hydrogeologic conditions, the U.S. Department of Energy (DOE), Fluor Hanford, Inc. (now CH2M Hill Plateau Remediation Company [CHPRC]), Pacific Northwest National Laboratory, and the Washington State Department of Ecology agreed that the long-term strategy for groundwater remediation at the 100-N Area should include apatite as the primary treatment technology. This agreement was based on results from an evaluation of remedial alternatives that identified the apatite permeable reactive barrier (PRB) technology as the approach showing the greatest promise for reducing 90Sr flux to the Columbia River at a reasonable cost. This letter report documents work completed to date on development of a high-concentration amendment formulation and initial field-scale testing of this amendment solution

Use of Polyphosphate to Decrease Uranium Leaching in Hanford 300 Area Smear Zone Sediments

The primary objective of this study is to summarize the laboratory investigations performed to evaluate short- and long-term effects of phosphate treatment on uranium leaching from 300 area smear zone sediments. Column studies were used to compare uranium leaching in phosphate-treated to untreated sediments over a year with multiple stop flow events to evaluate longevity of the uranium leaching rate and mass. A secondary objective was to compare polyphosphate injection, polyphosphate/xanthan injection, and polyphosphate infiltration technologies that deliver phosphate to sediment

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

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

SERDP ER-1376 Enhancement of In Situ Bioremediation of Energetic Compounds by Coupled Abiotic/Biotic Processes:Final Report for 2004 - 2006

This project was initiated by SERDP to quantify processes and determine the effectiveness of abiotic/biotic mineralization of energetics (RDX, HMX, TNT) in aquifer sediments by combinations of biostimulation (carbon, trace nutrient additions) and chemical reduction of sediment to create a reducing environment. Initially it was hypothesized that a balance of chemical reduction of sediment and biostimulation would increase the RDX, HMX, and TNT mineralization rate significantly (by a combination of abiotic and biotic processes) so that this abiotic/biotic treatment may be a more efficient for remediation than biotic treatment alone in some cases. Because both abiotic and biotic processes are involved in energetic mineralization in sediments, it was further hypothesized that consideration for both abiotic reduction and microbial growth was need to optimize the sediment system for the most rapid mineralization rate. Results show that there are separate optimal abiotic/biostimulation aquifer sediment treatments for RDX/HMX and for TNT. Optimal sediment treatment for RDX and HMX (which have chemical similarities and similar degradation pathways) is mainly chemical reduction of sediment, which increased the RDX/HMX mineralization rate 100 to150 times (relative to untreated sediment), with additional carbon or trace nutrient addition, which increased the RDX/HMX mineralization rate an additional 3 to 4 times. In contrast, the optimal aquifer sediment treatment for TNT involves mainly biostimulation (glucose addition), which stimulates a TNT/glucose cometabolic degradation pathway (6.8 times more rapid than untreated sediment), degrading TNT to amino-intermediates that irreversibly sorb (i.e., end product is not CO2). The TNT mass migration risk is minimized by these transformation reactions, as the triaminotoluene and 2,4- and 2,6-diaminonitrotoluene products that irreversibly sorb are no longer mobile in the subsurface environment. These transformation rates are increased 13 times further by chemical reduction of sediment. Dithionite reduction alone is not an effective treatment for TNT (intermediates that irreversibly sorb are not produced), even though the TNT degradation rate (to 2- or 4-aminodinitrotoluene) increases