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Treatment Study Plan for Nitrate Salt Waste Remediation Revision 1.0

The two stabilization treatment methods that are to be examined for their effectiveness in the treatment of both the unremediated and remediated nitrate salt wastes include (1) the addition of zeolite and (2) cementation. Zeolite addition is proposed based on the results of several studies and analyses that specifically examined the effectiveness of this process for deactivating nitrate salts. Cementation is also being assessed because of its prevalence as an immobilization method used for similar wastes at numerous facilities around the DOE complex, including at Los Alamos. The results of this Treatment Study Plan will be used to provide the basis for a Resource Conservation and Recovery Act (RCRA) permit modification request of the LANL Hazardous Waste Facility Permit for approval by the New Mexico Environment Department-Hazardous Waste Bureau (NMED-HWB) of the proposed treatment process and the associated facilities.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

OPC Paste Samples Exposed To Aggressive Solutions. Cementitious Barriers Partnership

The study presented in this report focused on a low-activity wasteform containing a high-pH pore solution with a significant level of sulfate. The purpose of the study was to improve understanding of the complex concrete/wasteform reactive transport problem, in particular, the role of pH in sulfate attack. Paste samples prepared at three different water-to-cement ratios were tested. The mixtures were prepared with ASTM Type I cement, without additional admixtures. The samples were exposed to two different sodium sulfate contact solutions. The first solution was prepared at 0.15M Na 2 SO 4 . The second solution also incorporated 0.5M NaOH, to mimic the high pH conditions found in Saltstone. The data collected indicated that, in Na 2 SO 4 solution, damage occurs to the pastes. In the case of the high-pH sulfate solution (Na 2 SO 4 + NaOH), no signs of damage were observed on any of the paste mixtures. These results indicate that the high sulfate content found in the wasteform pore solution will not necessarily lead to severe damage to concrete. Good-quality mixtures could thus prove durable over the long term, and act as an effective barrier to prevent radionuclides from reaching the environment.

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Transport properties of damaged materials. Cementitious barriers partnership

The objective of the Cementitious Barriers Partnership (CBP) project is to develop tools to improve understanding and prediction of the long-term structural, hydraulic, and chemical performance of cementitious barriers used in low-level waste storage applications. One key concern for the long-term durability of concrete is the degradation of the cementitious matrix, which occurs as a result of aggressive chemical species entering the material or leaching out in the environment, depending on the exposure conditions. The objective of the experimental study described in this report is to provide experimental data relating damage in cementitious materials to changes in transport properties, which can eventually be used to support predictive model development. In order to get results within a reasonable timeframe and to induce as much as possible uniform damage level in materials, concrete samples were exposed to freezing and thawing (F/T) cycles. The methodology consisted in exposing samples to F/T cycles and monitoring damage level with ultrasonic pulse velocity measurements. Upon reaching pre-selected damage levels, samples were tested to evaluate changes in transport properties. Material selection for the study was motivated by the need to get results rapidly, in order to assess the relevance of the methodology. Consequently, samples already available at SIMCO from past studies were used. They consisted in three different concrete mixtures cured for five years in wet conditions. The mixtures had water-to-cement ratios of 0.5, 0.65 and 0.75 and were prepared with ASTM Type I cement only. The results showed that porosity is not a good indicator for damage caused by the formation of microcracks. Some materials exhibited little variations in porosity even for high damage levels. On the other hand, significant variations in tortuosity were measured in all materials. This implies that damage caused by internal pressure does not necessarily create additional pore space in the microstructure, but likely creates new thin pathways between existing pore space for species to travel. These results have a significant impact on modeling efforts. Models relating porosity to tortuosity and permeability are unlikely to provide the correct basis for predicting long-term durability of concrete sustaining internal pressures and microcrack formation. Other avenues like the modeling of internal crystallization pressure need to be explored.

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Lawrence Livermore National Laboratory (LLNL) Hybrid-Energy Technology for Power and Industrial Heat with Near-Zero or Negative CO 2 Emissions

Major contributors to global CO 2 emissions include electricity (27%) and industry (23%), such as cement manufacturing (8%). Using post-combustion technology to reduce CO 2 emissions by 85-90% could increase the cost of generating electricity with fossil fuel by 40-70%, while increasing cement-manufacturing cost by 75-140%. Both sectors are under pressure to reduce CO 2 emissions and are seeking cost-effective, energy-efficient solutions to decarbonizing energy.

54 ENVIRONMENTAL SCIENCES↗

Solidification of SRPPF Aqueous Recovery Liquid: Process Disruptions

Savannah River National Laboratory has identified a magnesium oxysulfate grout formulation to solidify the liquid effluent from the Savannah River Plutonium Processing Facility (SRPPF) Aqueous Recovery System (ARS). The formulation uses reactive, light burnt MgO, anhydrous MgSO 4 , and dead burnt MgO and provides good mixability, similar density to the original Portland Cement-based mix, and a leachate pH of 9.39, within the assumed Waste Isolation Pilot Plant (WIPP) brine pH range. The formulation will solidify the effluent using a solid first, lost paddle design, within a 55-gallon drum. A series of seven different process disruptions, or irregular processing during the expected ARS liquid effluent solidification process, were completed to assess the severity of the impact of the process disruption and how the formulation behaves under these conditions. Seven process disruptions were investigated including: No Mixing, Partial Mixing, Compacted/Stratified, Sealed, Overfilled, Underfilled, and Undermixed. The impact on solidification, leachate pH, Er (a Pu/Am surrogate) distribution, and density of the resulting grout were established. Overall, four of the process disruptions, No Mixing, Partial Mixing, Compacted/Stratified, and Overfilled, resulted in basic, unabsorbed liquid that would require additional solidification to be acceptable for WIPP. Most solids generated in this testing met the expected WIPP leachate pH requirements. Solids from the Compacted/Stratified process disruption test, however, produced a leachate pH slightly above the assumed range in the WIPP performance assessment. The distribution of Er for most of the tests was relatively consistent. The No Mixing process disruption test, however, resulted in non-homogeneous Er distribution, indicating that radioactive material would not be evenly distributed throughout this solid’s matrix. The Overfilled test is the only mix with a density slightly below the acceptable value. The Sealed and Overmixed tests produced a solid closest to the standard mix with no unabsorbed liquid, expected leachate pH levels, consistent Er concentrations, and expected density, indicating these process disruptions do not have a negative impact on the final grout form. Based on the other process disruptions, it is critical to have premixed dry materials and a well-defined mixing process to produce a solid, homogeneous magnesium oxysulfate cement, with no unabsorbed liquid. These process disruption tests show that the lack of adequate mixing is fundamental to creating an improperly solidified material that may require remediation.

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Wellbore Integrity Network

In this presentation, we review the current state of knowledge on wellbore integrity as developed in the IEA Greenhouse Gas Programme's Wellbore Integrity Network. Wells are one of the primary risks to the successful implementation of CO{sub 2} storage programs. Experimental studies show that wellbore materials react with CO{sub 2} (carbonation of cement and corrosion of steel) but the impact on zonal isolation is unclear. Field studies of wells in CO{sub 2}-bearing fields show that CO{sub 2} does migrate external to casing. However, rates and amounts of CO{sub 2} have not been quantified. At the decade time scale, wellbore integrity is driven by construction quality and geomechanical processes. Over longer time-scales (> 100 years), chemical processes (cement degradation and corrosion) become more important, but competing geomechanical processes may preserve wellbore integrity.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

The Cementitious Barriers Partnership Experimental Programs and Software Advancing DOE’s Waste Disposal/Tank Closure Efforts – 15436

The U.S. Department of Energy Environmental Management (DOE-EM) Office of Tank Waste Management-sponsored Cementitious Barriers Partnership (CBP) is chartered with providing the technical basis for implementing cement-based waste forms and radioactive waste containment structures for long-term disposal. DOE needs in this area include the following to support progress in final treatment and disposal of legacy waste and closure of High-Level Waste (HLW) tanks in the DOE complex: long-term performance predictions, flow sheet development and flow sheet enhancements, and conceptual designs for new disposal facilities. The DOE-EM Cementitious Barriers Partnership is producing software and experimental programs resulting in new methods and data needed for end-users involved with environmental cleanup and waste disposal. Both the modeling tools and the experimental data have already benefited the DOE sites in the areas of performance assessments by increasing confidence backed up with modeling support, leaching methods, and transport properties developed for actual DOE materials. In 2014, the CBP Partnership released the CBP Software Toolbox –“Version 2.0” which provides concrete degradation models for 1) sulfate attack, 2) carbonation, and 3) chloride initiated rebar corrosion, and includes constituent leaching. These models are applicable and can be used by both DOE and the Nuclear Regulatory Commission (NRC) for service life and long-term performance evaluations and predictions of nuclear and radioactive waste containment structures across the DOE complex, including future SRS Saltstone and HLW tank performance assessments and special analyses, Hanford site HLW tank closure projects and other projects in which cementitious barriers are required, the Advanced Simulation Capability for Environmental Management (ASCEM) project which requires source terms from cementitious containment structures as input to their flow simulations, regulatory reviews of DOE performance assessments, and Nuclear Regulatory Commission reviews of commercial nuclear power plant (NPP) structures which are part of the overall US Energy Security program to extend the service life of NPPs. In addition, the CBP experimental programs have had a significant impact on the DOE complex by providing specific data unique to DOE sodium salt wastes at Hanford and SRS which are not readily available in the literature. Two recent experimental programs on cementitious phase characterization and on technetium (Tc) mobility have provided significant conclusions as follows: recent mineralogy characterization discussed in this paper illustrates that sodium salt waste form matrices are somewhat similar to but not the same as those found in blended cement matrices which to date have been used in long-term thermodynamic modeling and contaminant sequestration as a first approximation. Utilizing the CBP generated data in long-term performance predictions provides for a more defensible technical basis in performance evaluations. In addition, recent experimental studies related to technetium mobility indicate that conventional leaching protocols may not be conservative for direct disposal of Tc-containing waste forms in vadose zone environments. These results have the potential to influence the current Hanford supplemental waste treatment flow sheet and disposal conceptual design.

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Optimizing Geothermal Drilling: Oil and Gas Technology Transfer

There is a significant amount of financial risk associated with geothermal drilling. This study of drilling operations seeks opportunities to improve upon current practices and technologies. The scope of this study included analyzing 21 geothermal wells and 21 oil and gas wells. The goal was to determine a 'Perfect Well' using historical data to compare the best oil and gas well to the best geothermal well. Unfortunately, limitations encountered in the study included missing data (bit records, mud information, etc.) and poor data collection practices An online software database was used to format drilling data to IADC coded daily drilling reports and generate figures for analysis. Six major issues have been found in geothermal drilling operations. These problems include lost circulation, rig/ equipment selection, cementing, penetration rate, drilling program, and time management. As a result of these issues, geothermal drilling averaged 56.4 days longer than drilling comparable oil and gas wells in the wells in this study. Roughly $13.9 million was spent on non-productive time in the 21 geothermal wells, compared with only $1.3 million in the oil and gas wells, assuming a cost of $50,000 per day. Comparable events such as drilling the same sized hole, tripping in/out, cementing, and running the same size casing took substantially less time in the oil and gas wells. Geothermal wells were drilled using older and/or less advanced technology to depths less than 10,000 feet, while oil and gas wells reached 12,500 feet faster with purpose built rigs. A new approach is now underway that will optimize drilling programs throughout the drilling industry using Mechanical Specific Energy (MSE) as a tool to realize efficient drilling processes. Potential improvements for current geothermal operations are: the use of electronic records, real time services, and official glossary terms to describe rig operations, and advanced drilling rigs/technology.

15 GEOTHERMAL ENERGY↗

Development of a tool dedicated to the evaluation of hydrogen term source for technological Wastes: assumptions, physical models, and validation

In radioactive waste packages hydrogen is generated, in one hand, from the radiolysis of wastes (mainly organic materials) and, in the other hand, from the radiolysis of water content in the cement matrix. In order to assess hydrogen generation 2 tools based on operational models have been developed. One is dedicated to the determination of the hydrogen source term issues from the radiolysis of the wastes: the STORAGE tool (Simulation Tool Of Emission Radiolysis Gas), the other deals with the hydrogen source term gas, produced by radiolysis of the cement matrices (the Damar tool). The approach used by the STORAGE tool for assessing the production rate of radiolysis gases is divided into five steps: 1) Specification of the data packages, in particular, inventories and radiological materials defined for a package medium; 2) Determination of radiochemical yields for the different constituents and the laws of behavior associated, this determination of radiochemical yields is made from the PRELOG database in which radiochemical yields in different irradiation conditions have been compiled; 3) Definition of hypothesis concerning the composition and the distribution of contamination inside the package to allow assessment of the power absorbed by the constituents; 4) Sum-up of all the contributions; And finally, 5) validation calculations by comparison with a reduced sampling of packages. Comparisons with measured values confirm the conservative character of the methodology and give confidence in the safety margins for safety analysis report.

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Solidification/Stabilization of Liquid Oil Waste in Meta-kaolin-based geo-polymer - 17209

Cement-base solidification/stabilization (S/S) is a widely applied technique for the immobilization of inorganic hazardous constituents. However, S/S is considered less compatible with organic liquid wastes (OLW) because organic compounds may inhibit binder hydration. geo-polymers (alumino-silicate materials) are a worthwhile material for applications in which cements are inappropriate. In this study, we propose a direct immobilization process of organic liquid waste in a geo-polymer matrix based on the emulsification of OLW in an activating solution, followed by the addition of aluminosilicate source (meta-kaolin). At first, the harmlessness of the chemicals contained in the OLW on the geo-polymerization was examined through a screening, reveling that only acidic oils should be pre-treated before a direct immobilization. Waste form characterizations with a simulated OLW were measured, showing interesting mechanical and confinement properties. Waste forms containing 20% Vol. of OLW show a mechanical strength higher than 30 MPa in compression and less than 1 % of waste leached over a month in pure water. (authors)

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Test Methods for Cementitious Seal Materials for Borehole Disposal - 17352

The Nuclear and Energy Research Institute (IPEN-CNEN/SP) in Sao Paulo-Brazil, is considering borehole disposal of disused sealed radioactive sources (DSRS), which were used in smoke detectors, lightning arresters, radiotherapy, industrial gauges, irradiators, and other applications. The current IPEN concept of borehole is a modified BOSS system developed by the International Atomic Energy Agency (IAEA). It differs from the IAEA's design in that the disposal zone is below 300 m, and the DSRS are placed directly in the disposal packages constituted of stainless steel containers with 1.5 L capacity. A borehole drilled through sediment and granite, stabilized with stainless steel casing and cement grout is proposed for the conceptual model. Standard cement-material test methods and performance specific test methods, including accelerated aging methods, are needed for modeling the performance of the candidate cementitious grouts. A cross-disciplinary team from the USA Savannah River National laboratory is providing technical assistance to IPEN in this performance assessment. (authors)

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Retention of Cr in Meta-kaolin-based geo-polymeric Materials under Oxidation and Carbonation - 17453

Alkali activated alumino-silicates, often referred to as geo-polymers, are considered promising immobilization matrices for contaminants due to their high sorption capacity, durability and low leachability. For some contaminants they may prove superior to cement pastes that are conventional immobilization materials in waste management applications. However, estimating the retention capacity of some contaminants under environmental conditions that include oxidation and carbonation and may induce a valance change, is complicated. These contaminants tend to be soluble under oxidizing condition and form precipitates under reducing conditions. Thus, contaminant retention is highly dependent on the initial oxidation state at which the metal was introduced, as well as the matrix sorption ability, ability to resist oxidation and carbonation, and the contaminant leachability. Moreover, carbonation in considered one of the most important degradation mechanisms in cementitious material, causing porosity reduction and significant changes in contaminant leachability, however, geo-polymers have considerably lower Ca content relative to cements, or none, and the effect of carbonation on these pastes is less clear. Thus, contaminant release mechanisms and rates must be estimated based upon exposure to various atmospheres appropriate to waste management applications. In this study we aim to estimate the sorption capacity, and leachability of Cr from a meta-kaolin based geo-polymer, doped with Cr, as a function of its oxidation state and carbonation. Cr has a high valance range from +6 to 0 similar to Tc, and is used as its simulant in the current study. Sodium dichromate was used as an oxidized source metal material. To induce reducing conditions, ascorbic acid was added except for experimental control cases. The samples were aged under N{sub 2}, 98% N{sub 2} + 2% CO{sub 2}, CO{sub 2} deficient air and air environments under constant relative humidity. Following aging, samples were subject to equilibrium leaching as a function of pH (EPA Method 1313) and monolith mass transport rate testing (EPA Method 1315). Mass balance calculations, based on the results of a pH dependent leaching test, have shown that oxidized Cr samples lost 85-95% of their Cr content, whereas, the reduced Cr samples lost only 20% of their Cr content. On the other hand, the leachability of Si and Al is much higher in the reduced-Cr samples then in the samples with oxidized Cr, and their natural pH is up to 2.5 pH units lower than that of the oxidizing cases. Thus, we conclude that the combination of the reducing agent and the spike chemistry influence the matrix formation. Sample aging have not resulted in any significant change in the Cr-leaching behavior of the oxidizing matrices in the pH dependent leaching test, although a significant decrease in the natural pH, of 1.5 pH unit, was observed upon exposure to elevated CO{sub 2} levels (2%), probably due to the formation of Na-carbonate species. The pH and leaching behavior of the reduced Cr samples under the various aging conditions have not yielded significant variation either in their natural pH or in their leaching behavior. (authors)

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The cementitious barriers partnership experimental programs and software advancing DOE's waste disposal/tank closure efforts - 15436

The U.S. Department of Energy Environmental Management (DOE-EM) Office of Tank Waste Management sponsored Cementitious Barriers Partnership (CBP) is chartered with providing the technical basis for implementing cement-based waste forms and radioactive waste containment structures for long-term disposal. DOE needs in this area include the following to support progress in final treatment and disposal of legacy waste and closure of High-Level Waste (HLW) tanks in the DOE complex: - Long-term performance predictions and - Flow sheet development and flow sheet enhancements - Conceptual designs for new disposal facilities The DOE-EM Cementitious Barriers Partnership is producing software and experimental programs resulting in new methods and data needed for end-users involved with environmental cleanup and waste disposal. Both the modeling tools and the experimental data have already benefited the DOE sites in the areas of performance assessments by increasing confidence backed up with modeling support, leaching methods, and transport properties developed for actual DOE materials. In 2014, the CBP Partnership released the CBP Software Toolbox - 'Version 2.0' which provides concrete degradation models for: 1) sulfate attack, 2) carbonation, 3) chloride initiated rebar corrosion, and includes constituent leaching. These models are applicable and can be used by both DOE and the Nuclear Regulatory Commission (NRC) for service life and long-term performance evaluations and predictions of nuclear and radioactive waste containment structures across the DOE complex (Figure 1) including Future SRS salt-stone and HLW tank performance assessments and special analyses - Hanford site HLW tank closure projects and other projects in which cementitious barriers are required - The Advanced Simulation Capability for Environmental Management (ASCEM) project which requires source terms from cementitious containment structures as input to their flow simulations - Regulatory reviews of DOE performance assessments - Nuclear Regulatory Commission reviews of commercial nuclear power plant (NPP) structures which are part of the overall US Energy Security program to extend the service life of NPPs In addition, the CBP experimental programs have had a significant impact on the DOE complex by providing specific data unique to DOE sodium salt wastes at Hanford and SRS which are not readily available in the literature. Two recent experimental programs on cementitious phase characterization and on technetium (Tc) mobility have provided significant conclusions as summarized below: Recent mineralogy characterization discussed in this paper illustrates that sodium salt waste form matrices are somewhat similar to but not the same as those found in blended cement matrices which to date have been used in long-term thermodynamic modeling and contaminant sequestration as a first approximation. Utilizing the CBP generated data in long-term performance predictions provides for a more defensible technical basis in performance evaluations. - In addition, recent experimental studies related to technetium mobility indicate that conventional leaching protocols may not be conservative for direct disposal of Tc- containing waste forms in vadose zone environments. These results have the potential to influence the current Hanford supplemental waste treatment flow sheet and disposal conceptual design. (authors)

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Simulating field conditions for the curing of salt-stone - 15501

salt-stone is a cementitious, low-level waste (LLW) material processed and stored at the Savannah River Site (SRS). It consists of fly ash (FA), blast furnace slag (BFS), and Portland cement that are blended with LLW salt solution. The dry feed materials and the salt solution are mixed at the salt-stone Production Facility (SPF), and the fresh grout subsequently pumped into a salt-stone Disposal Unit (SDU) in the salt-stone Disposal Facility (SDF) where it cures to form a rigid, cementitious monolith. In order to demonstrate the long-term performance of salt-stone, non-radioactive simulant samples are processed and cured in a laboratory environment and subsequently tested with respect to key performance properties. Of particular relevance to assessing the long-term stabilization and immobilization of radionuclides in salt-stone is the permeability, or saturated hydraulic conductivity, which determines the rate of infiltration for oxygen-bearing ground waters that can affect redox sensitive contaminants, such as {sup 99}Tc. Environmental conditions in the SDU, in particular temperature and humidity, are believed to affect the cured properties of salt-stone. With respect to humidity it has been determined that the average vapor space humidity in an SDU is at least 95%, and in addition the assumption can be made that underlying grout is subjected to a moisture-saturated environment by the grout poured over it. With respect to temperature, the SDUs contain thermo-well arrays that provide detailed vertical, and to a lesser degree radial, temperature profiles. Temperature data from the SDUs have subsequently been utilized to better simulate curing temperatures for simulant salt-stone in the laboratory. However, no two thermal profiles are the same, varying with respect to the following parameters: initial temperature, rate of temperature increase, maximum temperature attained, time at maximum temperature, and cooling rate. These temperature variables are dependent on the depth of grout (due to insulating effects of underlying and overlying grout), frequency of grout addition to the SDU (with more frequent additions causing grout temperatures to rise due to the exothermic hydration reactions), and, to a lesser degree, the ambient temperature of the external environment. Due to the variability in each thermal profile recorded in an SDU, the question arises as to which profile (or profiles) should be used in the simulated laboratory environment to best mimic the curing of field emplaced salt-stone, such that there is confidence that the properties measured for laboratory-prepared samples are representative of the grout in the SDU. Since the current SDU design contains sixty-six thermo-wells it is obviously not practical to process simulant samples according to each profile. Rather the aim would be to choose a reduced number of profiles that adequately encompass the range of recorded profiles, or to choose a single profile that is considered most conservative with respect to the resulting properties of interest. This is typically thought to be the profile exhibiting the highest peak temperature since for cement-based materials higher curing temperatures (> 60 deg. C), while resulting in enhanced reaction kinetics and strength development for short curing durations (∼28 days), have been shown to adversely affect the physical properties of the material after extended cure times. In choosing representative profiles it is important to consider not only the maximum temperature, but also the influence of rate of temperature rise to the maximum temperature, and time at or close to the maximum temperature on the post-cured properties. The intent of this paper is to consider the varied curing temperature profiles to which the salt-stone is exposed in an SDU, and to analyze the currently available data for elevated temperature curing of salt-stone to determine the potential thermal effects on the saturated hydraulic conductivity of salt-stone emplaced in an SDU. This may subsequently facilitate a more informed approach to simulating the curing of salt-stone in a laboratory environment. (authors)

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NDA Challenges during Cleanup of the Hanford 618-10 Burial Ground Trenches - 15542

The 618-10 Burial Ground on the Hanford Reservation was an early trench waste site used for the disposal of waste from the 300 Area at Hanford. Much of this waste consisted of residues from evaluations of failed fuel as well as various process and separations studies associated with the Department of Energy (DOE) mission which were performed in the 300 Area between March 1954 and September 1963. Much of this waste contained significant concentrations of fission products as well as Transuranic (TRU) radionuclides. Waste forms consist of drums and boxes which were disposed of in the trenches. Many of the drums are shielded containers, cemented sludge, or cemented debris. There are no identifying marks on the containers to correlate them to a specific waste stream. In addition there is some waste in the trenches which came from other locations outside of the 300 area. Cleanup of the 618-10 burial ground is covered under the Washington Closure Hanford (WCH) contract. Due to the proximity of the 618-10 site to the Columbia River, waste is being removed from the 618-10 site, stabilized, and disposed of into either the Environmental Restoration Disposal Facility (ERDF) if the containers are determined to be LLW or transferred to the Hanford Central Waste Complex (CWC) if the containers are suspected to be TRU waste. In order to determine the correct disposal path Non Destructive Assay (NDA) must be performed on all of the containers excavated from the trenches. The NDA of these containers is performed using germanium gamma spectroscopy with an In Situ Object Counting System (ISOCS) and with a neutron slab counter. Due to the challenges associated with these difficult waste streams, matrices, and lack of information to associate these containers with a particular process, the NDA program has had to develop a more robust process to ensure the correct disposition of the waste. (authors)

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Laser-Induced Breakdown Spectroscopy for Contamination Detection in Concrete on Nuclear Facilities - 18296

Laser-Induced Breakdown Spectroscopy (LIBS) provides a real-time analytical technique for determining the elemental composition of a sample. This work was carried out to determine the suitability of the method for contamination detection in concrete. Cement paste samples were cast, containing simulant radionuclide contaminant salts of Co and Ni at 0.1 wt% inclusion. LIBS was then carried out on the samples, and contaminated samples compared to an uncontaminated ordinary portland cement (OPC) reference. A ratio of normalised peak intensities was used to determine differences in spectra between the samples. Where differences between sample and reference spectra were discovered, the National Institute of Standards and Technology spectral lines database was consulted, the identity of the contaminants could be confirmed, and Co and Ni were both identified at less than 0.1 wt% inclusion. (authors)

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International Implementation of IAEA's Borehole Disposal Concept for Sealed Radioactive Sources - 18545

With funding from the Government of Canada, and support from the U.S. Nuclear Regulatory Commission's (NRC's) Office of International Program and many others, the International Atomic Energy Agency (IAEA) is supporting the field deployment of the Borehole Disposal Concept (BDC) for secure disposal of radioactive sources in Ghana, the Philippines and Malaysia. This is a first-of-its-kind implementation. Though small in volume, disused sealed radioactive sources can be intensively radioactive and create a significant safety and security liability for the majority of the 168 Member States in the IAEA. Millions of sealed radioactive sources have been manufactured since 1901, and it is estimated that hundreds of thousands are now unwanted. The irony is that some of the countries with the smallest inventories have the greatest difficulties managing their radioactive wastes. The BDC was originally conceptualized in an IAEA-study undertaken by the South African Nuclear Energy Corporation (NECSA) for countries with small inventories of disused sealed radioactive sources. There are multiple, passive engineered and natural barriers in the BDC design, including an inner stainless-steel capsule (which holds the wastes), an inner cement containment barrier, an outer stainless steel container and outer backfill cement, as well as the surrounding geosphere. In common subsurface geochemical environments, these barriers will isolate the wastes from the biosphere, provide effective containment and ensure long-term safety. To greatly limit the likelihood of inadvertent human intrusion (safety), and deliberate human intrusion (security), these waste packages will be disposed of in a narrow diameter borehole (26 cm) at depths greater than 30 m. This type of borehole disposal creates an exceptionally small footprint, removes the wastes from normal human surficial activities, and isolates the waste packages from near-surface processes. Over the past 20 years, the IAEA, NECSA and many others have advanced the BDC on the shoulders of the IAEA's broader work supporting safe and secure disposal of radioactive wastes and management of sealed radioactive sources. With recent funding and support from many others, the IAEA has assisted Ghana, Malaysia and the Philippines in assessing their inventories and conditioning their disused sealed radioactive sources, in drilling investigation boreholes and characterizing their proposed sites, and in designing their disposal systems. These countries plan to place the uppermost waste package at depths greater than 100 m. While activities in the Philippines remain focused on-site characterization, Ghana is in the latter stages of developing their Safety Case for operational and 'post-closure' safety and Malaysia has completed their Safety Case and submitted a license application to construct and operate a BDC facility. Though this paper identifies the support provided to Member States by the IAEA, it is the Ghana Atomic Energy Commission and the Malaysian Nuclear Agency that are responsible for the safety and security of the disposals and that have been responsible for carrying-out their disposal programs. Once the BDC is licensed by the relevant national regulatory bodies, these first-of-a-kind disposal approaches will provide a template for other countries to safely dispose of their disused sealed radioactive sources - permanently eliminating their safety and security liabilities. (authors)

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Mercury Speciation and Stabilization in Saltstone - 19103

Mercury is a contaminant of concern in Savannah River Site (SRS) high level waste (HLW). For five decades elemental mercury was used in the catalytic dissolution of aluminum cladding from the enriched-alloy uranium recovery process. Over 60,000 kg of mercury are now distributed in the SRS HLW tanks. The mercury speciation in the liquid waste streams resulting from conditioning HLW sludge for vitrification and in the decontaminated low activity sodium salt solution removed from the tanks was initially thought to be primarily ionic with a minor amount of elemental mercury. Recent sampling detected organic mercury, primarily methylmercury, HgCH{sub 3}{sup +} (MeHg{sup +}), and a trace amount of ethylmercury (EtHg) in these streams in addition to the ionic and elemental forms of mercury. The objective of this work was to identify the fate of the organic mercury in saltstone, a waste form containing portland cement, slag cement, and Class F fly ash. This information is needed to evaluate total mercury and organic mercury limits for the saltstone Waste Acceptance Criteria to assure regulatory compliance with mixed waste disposal requirements and to evaluate opportunities to enhance the waste form performance. Results to date indicate that the MeHg{sup +} reacts with sulfide in the cementitious reagents, slag in particular, to form nanoparticles of β-HgS, meta cinnabar, which is very insoluble and has a solubility product in water, pK{sub sp}, at 25 deg. C of 53. (authors)

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