Kent E. Parker

Characterization of Vadose Zone Sediment: Uncontaminated RCRA Borehole Core Samples and Composite Samples

This report was revised in September 2008 to remove acid-extractable sodium data from Tables 4.14, 4.16, 5.20, 5.22, 5.43, and 5.45. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in February 2002. The overall goal of the of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities. To meet this goal, CH2M HILL Hanford Group, Inc. asked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediment from within the S-SX Waste Management Area. This report is one in a series of four reports to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from Resource Conservation and Recovery Act (RCRA) borehole bore samples and composite samples.

Sequestration and retention of uranium(VI) in the presence of hydroxylapatite under dynamic geochemical conditions

Environmental context. Contamination of surface and subsurface geologic media by heavy metals and radionuclides is a significant problem within the United State Department of Energy complex as a result of past nuclear operations. Numerous phosphate-based remediation strategies have been proposed to introduce hydroxylapatite directly or indirectly (i.e. through in situ precipitation) into subsurface regimes to act as an efficient sorbent for sequestration of metals and radionuclides such as uranium. Results presented here illustrate the importance of variable geochemical conditions on the mechanism of sequestration and long-term retention of uranium in the presence of hydroxylapatite. Abstract. Numerous solid- and aqueous-phase phosphate-based technologies for remediating heavy metals and radionuclides have the common premise of sequestration by hydroxylapatite. Complexation reactions and hydrolysis generally preclude actinides from incorporation into intracrystalline sites; rather, surface sorption and precipitation are significant mechanisms for the sequestration of actinides. The effect of pH, aqueous speciation, and the availability of reactive surface sites on minerals such as hydroxylapatite have a significant impact on the mechanism and degree of sequestration and retention of variably charged contaminants such as uranium. Yet, little attention has been given to the sequestration and retention of uranium by hydroxylapatite under dynamic geochemical conditions that may be encountered during remediation activities. We present the results of an investigation evaluating the removal of uranium by hydroxylapatite in systems near equilibrium with respect to hydroxylapatite, and the effect of dynamic aqueous geochemical conditions, such as those encountered during and subsequent to remediation activities, on the retention of uranium. Results presented here support previous investigations demonstrating the efficiency of hydroxylapatite for sequestration of uranium and illustrate the importance of geochemical conditions, including changes to surface properties and aqueous speciation, on the sequestration and retention of uranium.

Interim Report: Uranium Stabilization Through Polyphosphate Injection - 300 Area Uranium Plume Treatability Demonstration Project

This report presents results from bench-scale treatability studies conducted under site-specific conditions to optimize the polyphosphate amendment for implementation of a field-scale technology demonstration to treat aqueous uranium within the 300 Area aquifer of the Hanford site. The general treatability testing approach consists of conducting studies with site sediment and under site conditions, in order to develop an effective chemical formulation for the polyphosphate amendments and evaluate the transport properties of these amendments under site conditions. Phosphorus-31 (31P) NMR was utilized to determine the effects of Hanford groundwater and sediment on the degradation of inorganic phosphates. Static batch tests were conducted to optimize the composition of the polyphosphate formulation for the precipitation of apatite and autunite, as well as to quantify the kinetics, loading and stability of apatite as a long-term sorbent for uranium. Dynamic column tests were used to further optimize the polyphosphate formulation for emplacement within the subsurface and the formation of autunite and apatite. In addition, dynamic testing quantified the stability of autunite and apatite under relevant site conditions. Results of this investigation provide valuable information for designing a full-scale remediation of uranium in the 300 aquifer.

Secondary Waste Form Development and Optimization—Cast Stone

Washington River Protection Services is considering the design and construction of a Solidification Treatment Unit (STU) for the Effluent Treatment Facility (ETF) at Hanford. The ETF is a Resource Conservation and Recovery Act-permitted, multi-waste, treatment and storage unit and can accept dangerous, low-level, and mixed wastewaters for treatment. The STU needs to be operational by 2018 to receive secondary liquid wastes generated during operation of the Hanford Tank Waste Treatment and Immobilization Plant (WTP). The STU to ETF will provide the additional capacity needed for ETF to process the increased volume of secondary wastes expected to be produced by WTP.

300 Area Treatability Test: Laboratory Development of Polyphosphate Remediation Technology for In Situ Treatment of Uranium Contamination in the Vadose Zone and Capillary Fringe

A laboratory testing program has been conducted to optimize polyphosphate remediation technology for implementation through a field-scale technology infiltration demonstration to stabilize soluble, uranium-bearing source phases in the vadose zone and capillary fringe. Source treatment in the deep vadose zone will accelerate the natural attenuation of uranium to more thermodynamically stable uranium-phosphate minerals, enhancing the performance of the proposed polyphosphate remediation within the 300 Area aquifer. The objective of this investigation was to develop polyphosphate remediation technology to treat uranium contamination contained within the deep vadose zone and capillary fringe. This chapter presents the results of an investigation that evaluated the rate and extent of reaction between polyphosphate and the uranium mineral phases present within the 300 Area, and autunite formation as a function of polyphosphate formulation and concentration. This information is critical for identifying the optimum implementation approach and controlling the flux of uranium to the underlying aquifer during remediation. Results from this investigation may be used to design a full-scale remediation of uranium at the 300 Area of the Hanford Site.

Characterization of Vadose Zone Sediments Below the C Tank Farm: Borehole C4297 and RCRA Borehole 299-E27-22

The overall goal of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities at Hanford. To meet this goal, CH2M HILL Hanford Group, Inc. tasked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediments from within Waste Management Area (WMA) C. This report is the first of two reports written to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from borehole C4297, installed adjacent to Tank C-105, and from borehole 299-E27-22, installed directly north of the C Tank Farm. Sediments from borehole 299-E27-22 were considered to be background uncontaminated sediments against which to compare contaminated sediments for the C Tank Farm characterization effort. This report also presents our interpretation of the data in the context of sediment types, the vertical extent of contamination, the migration potential of the contaminants, and the likely source of the contamination in the vadose zone and groundwater below the C Tank Farm. The information presented in this report supports the A-AX, C and U Waste Management Area field investigation report(a) in preparation by CH2M HILL Hanford Group, Inc. A core log was generated for both boreholes and a geologic evaluation of all core samples was performed at the time of opening. Aliquots of sediment from the borehole core samples were analyzed and characterized in the laboratory for the following parameters: moisture content, gamma-emitting radionuclides, one-to-one water extracts (which provide soil pH, electrical conductivity, cation, trace metal, and anion data), total carbon and inorganic carbon content, and 8 M nitric acid extracts (which provide a measure of the total leachable sediment content of contaminants). Two key radiocontaminants, technetium-99 and uranium-238, along with other trace metals were determined in acid and water extracts by inductively coupled plasma mass spectrometry.

Secondary Waste Form Screening Test Results—THOR® Fluidized Bed Steam Reforming Product in a Geopolymer Matrix

Screening tests are being conducted to evaluate waste forms for immobilizing secondary liquid wastes from the Hanford Tank Waste Treatment and Immobilization Plant (WTP). Plans are underway to add a stabilization treatment unit to the Effluent Treatment Facility to provide the needed capacity for treating these wastes from WTP. The current baseline is to use a Cast Stone cementitious waste form to solidify the wastes. Through a literature survey, DuraLith alkali-aluminosilicate geopolymer, fluidized-bed steam reformation (FBSR) granular product encapsulated in a geopolymer matrix, and a Ceramicrete phosphate-bonded ceramic were identified both as candidate waste forms and alternatives to the baseline. These waste forms have been shown to meet waste disposal acceptance criteria, including compressive strength and universal treatment standards for Resource Conservation and Recovery Act (RCRA) metals (as measured by the toxicity characteristic leaching procedure [TCLP]). Thus, these non-cementitious waste forms should also be acceptable for land disposal. Information is needed on all four waste forms with respect to their capability to minimize the release of technetium. Technetium is a radionuclide predicted to be in the secondary liquid wastes in small quantities, but the Integrated Disposal Facility (IDF) risk assessment analyses show that technetium, even at low mass, produces the largest contribution to the estimated IDF disposal impacts to groundwater.

Effect of Concrete Wasteform Properties on Radionuclide Migration

The objective of this investigation was to initiate numerous sets of concrete-soil half-cell tests to quantify 1) diffusion of I and Tc from concrete into uncontaminated soil after 1 and 2 years, 2) I and Re (set 1) and Tc (set 2) diffusion from fractured concrete into uncontaminated soil, and 3) evaluate the moisture distribution profile within the sediment half-cell. These half-cells will be section in FY2009 and FY2010. Additionally, 1) concrete-soil half-cells initiated during FY2007 using fractured prepared with and without metallic iron, half of which were carbonated using carbonated, were sectioned to evaluate the diffusion of I and Re in the concrete part of the half-cell under unsaturated conditions (4%, 7%, and 15% by wt moisture content), 2) concrete-soil half cells containing Tc were sectioned to measure the diffusion profile in the soil half-cell unsaturated conditions (4%, 7%, and 15% by wt moisture content), and 3) solubility measurements of uranium solid phases were completed under concrete porewater conditions. The results of these tests are presented.

Carbon Tetrachloride Partition Coefficients Measured by Aqueous Sorption to Hanford Sediments from Operable Units 200-UP-1 and 200-ZP-1

Kd values obtained on sediment samples from 200-UP-1 and 10-ZP-1 contribute to a larger Kd database that exists for other Hanford sediments, and contains significant desorption data for CCl4. Adsorption results presented here validate the use of a linear adsorption isotherm (Kd) to predict short contact time CCl4 adsorption to sediments in 200-UP-1 groundwater plume for a distinct ranges in CCl4 concentration. However, this does not imply that values of Kd will be constant if the groundwater chemical composition at 200-UP-1 changes with space or time. Additionally, results presented here suggest the potential significance of slower intraparticle diffusion on the long-term fate of CCl4 within the subsurface Hanford environment. Such behavior could afford prolonged desorption of CCl4 and serve as a long-term source of contaminant CCl4 to the aquifer. Further evaluation of possible bimodal sorption behavior for CCl4 and the mechanism of CCl¬4 sequestration should be the subject of future investigations to provide a thorough, mechanistic understanding of the retention and long-term fate of CCl4. Comparison of previous data with new results (e.g., from this study) will allow inferences to be made on how the 200-UP-1 Kd values for CCl4 may compare with sediments from other Hanford locations. This site-specific sorption data, when complemented by the chemical, geologic, mineralogic, hydrologic, and physical characterization data that are also being collected (see Sampling and Analysis Plan for the 200-UP-1 Groundwater Monitoring Well Network, DOE 2002) can be used to develop a robust, scientifically defensible data base to allow risk predictions to be generated and to aid in future remediation decisions for the 200-UP-1 and 200-ZP-1 operable units.

Removal of Mercury from Aqueous Streams of Fossil Fuel Power Plants Using Novel Functionalized Nanoporous Sorbents

A new class of hybrid nanoporous materials has been developed at the Pacific Northwest National Laboratory for removing toxic heavy metals such as mercury from aqueous and nonaqueous waste streams. These novel materials consist of functional molecules capable of selectively binding mercury (thiol groups) covalently bound (as densely populated monolayers) to the synthetic nanoporous substrates. Tests indicated that this sorbent (Self-Assembled Monolayers on Mesoporous Silica—SAMMS) can achieve mercury loading as high as ∼635 mg/g. The high affinity for Hg adsorption by this material was reflected by Kd values as high as 3.5 × 108 ml/g. Data indicated that SAMMS can adsorb both inorganic and organic forms of mercury. Experimental data indicated that mercury adsorption performance of SAMMS was not significantly affected by pH, ionic strength, presence of other cations (Na, Ca, Cd, Cu, Fe, Ni, Pb, and Zn), and complexing anions (Cl, CN, CO3, SO4, and PO4) in solution. Adsorption kinetics studies indicated that SAMMS adsorbed mercury very rapidly (about 99.9% adsorption occurring within first five minutes). Tests conducted using samples of different aqueous and non-aqueous waste streams have confirmed the exemplary performance characteristics of SAMMS sorbents. Preliminary cost estimates indicated that using SAMMS would result in significant savings in mercury remediation costs as compared to the use of conventional adsorbents such as ion exchange resin and activated carbon.