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At least 937 records · Page 52

Spectroscopic Properties of Tc(I) Tricarbonyl Species Relevant to the Hanford Tank Waste

Technetium-99 (Tc) exists predominately in soluble forms in the liquid supernatant and salt cake fractions of the nuclear tank waste stored at the U.S. DOE Hanford Site. In the strongly alkaline environments prevalent in the tank waste, its dominant chemical form is pertechnetate (TcO4-, oxidation state +7). However, attempts to remove Tc from the Hanford tank waste using ion-exchange processes specific to TcO 4 - only met with limited success, particularly processing tank waste samples containing elevated concentrations of organic complexants. This suggests that a significant fraction of the soluble Tc can be present as non-pertechnetate low-valent Tc (oxidation state < +7) (non-pertechnetate). The chemical identities of these non-pertechnetate species are poorly understood. Previous analysis of the SY-101 and SY-103 tank waste samples provided strong evidence that non-pertechnetate can be comprised of [Tc(CO) 3 ] + complexes containing Tc in oxidation state +1 (Lukens et al. 2004). During the last two years, our team has expanded this work and demonstrated that high-ionic-strength solutions typifying tank waste supernatants promote oxidative stability of the [Tc(CO) 3 ] + species (Rapko et al. 2013; Levitskaia et al. 2014). It also was observed that high-ionic-strength alkaline matrices stabilize Tc(VI) and potentially Tc(IV) oxidation states, particularly in presence organic chelators, suggesting that the relevant Tc compounds can serve as important redox intermediates facilitating the reduction of Tc(VII) to Tc(I). Designing strategies for effective Tc processing, including separation and immobilization, necessitates understanding the molecular structure of these non-pertechnetate species and their identification in the actual tank waste samples. To-date, only limited information exists regarding the nature and characterization of the Tc(I), Tc(IV), and Tc(VI) species. One objective of this project is to identify the form of non-pertechnetate in the Hanford waste. To do this, we are developing a spectral library of reference non-pertechnetate compounds that can be compared against actual waste samples. The emphasis of the fiscal year 2015 work was Tc(I) tricarbonyl [Tc(CO) 3 ] + compounds. The key findings are summarized below.

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Chlorinolysis reclaims rubber of waste tires

Process reclaims rubber and reduces sulfur content by using chlorine gas to oxidize sulfur bonds in preference to other bonds. Rubber does not have poor hysteresis and abrasion resistance like conventionally reclaimed rubber and is suitable for premium radial tires. Chlorinated rubber is less susceptible to swelling by oils and may be used as paint ingredient.

Dufresne, E. R.↗

Dehalogenation of electrochemical processing salt simulants with ammonium phosphates and immobilization of salt cations in an iron phosphate glass waste form

This study demonstrates the conversion of simulated pyroprocessing salt wastes [i.e., ER(SF) and ERV2] into chemically durable iron phosphate glass waste forms through reactions with ammonium hydrogen phosphate precursors [i.e., NH4H2PO4 and (NH4)2HPO4] and added Fe2O3. The reaction of the salt simulants with the phosphate precursors resulted in dehalogenation of the salt through the production of NH4Cl and NH4I (along with water), of which the NH4Cl can be used to produce UCl3 oxidant for use in the electrorefiner during pyroprocessing. These iron phosphate glasses contain a notably higher waste loading than the baseline glass-bonded sodalite ceramic waste form, which requires about 70 vol% sodalite to accommodate Cl from the salt, because they are dehalogenated prior to vitrification. The high waste loadings coupled with higher bulk densities (~3×103 kg/m3) than glass-bonded sodalite (~2.3×103 kg/m3) mean that these glasses have a higher storage volume, i.e., the volume required to immobilize a given mass of waste. The iron phosphate glass waste forms were characterized using a variety of techniques including physical property measurements and chemical durability testing. Following initial testing, a proof-of-concept demonstration was conducted to show that the NH4Cl generated from this process could be used to produce UCl3 using depleted uranium dendrites as a feedstock.

phosphate glass, pyroprocessing, waste forms, salt↗

Real Time, In-line Monitoring of Hanford Tank Wastes - Year 1 Report

The team comprised of students, postdocs, early, mid and senior career scientists from Los Alamos National Laboratory, Savanah River National Laboratory, Georgia Tech and Florida International University, with the guidance of H2C, is developing a suite of in-line instruments for the Hanford high level waste (HLW) and low active waste (LAW) processes to provide near-real-time analysis of waste form physical properties and composition. The work builds on results from the recent DOE-ORP, EM Technology Development and other projects that demonstrated promise for the use of real-time in-line monitoring (RTIM) to measure chemical compositions of slurries of up to 20 weight % solids. The goal is for this instrument suite is to substantially reduce the need for sampling for process control. Sample waste, exposure associated with sample analysis, and the demand for an external laboratory facility would be greatly reduced. The throughput of waste treatment systems would be improved by elimination of the downtime caused by waiting for sample results. This translates into reduced process storage as process knowledge will be continuously updated in near-real-time. These breakthrough technologies would significantly reduce the life cycle cost and accelerate the schedule for the Hanford tank waste mission.

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Direct Processing of Lithium Chloride Based Waste Salt in a Ceramic Waste Form

Ceramic waste form materials were fabricated with a LiCl based salt mixture to demonstrate the suitability of direct processing of waste salt from an all LiCl pyroprocessing flow sheet on the formation, microstructure, and durability of ceramic waste forms. Materials were successfully synthesized by using the simplified direct processing technique with salt loadings of 5, 7.5, and 10 wt% at the laboratory scale. Materials fabricated with LiCl based salt indicated full conversion of zeolite to sodalite occurred to form products with low open porosity. This indicates that the Na 2 O content of NBS4 glass is suitable for processing salt chemistries which do not contain NaCl. Generated sodalite was microencapsulated by the glass binder, halite occlusions were detected within sodalite domains at all salt loadings, and a Cs-rich phase believed to be Cs-pollucite was detected in the material made with the lowest salt loading (5 wt%). Salt inclusions were encapsulated within the binder glass at all loadings, and found to consist primarily of NaCl with Cs present. A small amount of salt was found at the surface of the wasteform made with the highest salt loading of 10 wt%, which may indicate an upper limit to the amount of salt that can be accommodated or incomplete mechanical mixing of the reagents. Durability testing by using the ASTM C1308 method indicated that initial rapid dissolution of exposed halite inclusion phases was directly correlated to salt loading. Wasteform degradation during all tests occurred primarily due to dissolution of the sodalite phase. Durability of the binder glass was found to increase as the waste salt loading increased. Results for the release of cations from the salt indicate the changes in wasteform durability and halite inclusion chemistry are strongly influenced by ion exchange phenomena between the salt and the glass. This appears to be the result of the relatively stronger affinity for the glass phase of Li, compared to that of other cations such as Na and Cs. The effects from cation exchange were diminished at lower salt loadings.

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Panel Session 120: Roundtable: Waste Management - Energy Facilities Contractor Operating Group (EFCOG WM)

This Roundtable focused on the WM EFCOG working group as they met to discuss a variety of issues of importance to US DOE waste management operations. The purpose of the WM EFCOG is to seek out and promote the best management and operating practices, cost effective technologies and disposal options for all waste streams generated at US DOE facilities whether destined for US DOE or commercial facilities. Each site representative provided a radioactive waste management lessons learned briefing. Panelists with presentations: Savannah River Site (SRS) Solid Waste Program Update (Kerri Crawford); Idaho Clean-up Project Status (Frederick Hughes); West Valley Demonstration Project Update - EFCOG Waste Management Working Group (John Rendall); Key Project Challenges and Successes (Kalli Shupe); EFCOG WMWG Challenging Waste Subgroup Update (Tammy Monday); CH TRU Difficult Waste Stream Processing Challenges (Daniel Pancake); Argonne Building 350 Clean-up Success Using Effective Work Control (Daniel Dilday); Problematic Waste Streams on the Oak Ridge Reservation (John Wrapp)

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Exploring Engineering Control through Process Manipulation of Radioactive Liquid Waste Tank Chemical Cleaning

One method of remediating legacy liquid radioactive waste produced during the cold war, is aggressive in-tank chemical cleaning. Chemical cleaning has successfully reduced the curie content of residual waste heels in large underground storage tanks; however this process generates significant chemical hazards. Mercury is often the bounding hazard due to its extensive use in the separations process that produced the waste. This paper explores how variations in controllable process factors, tank level and temperature, may be manipulated to reduce the hazard potential related to mercury vapor generation. When compared using a multivariate regression analysis, findings indicated that there was a significant relationship between both tank level (p value of 1.65x10 -23 ) and temperature (p value of 6.39x10 -6 ) to the mercury vapor concentration in the tank ventilation system. Tank temperature showed the most promise as a controllable parameter for future tank cleaning endeavors. Despite statistically significant relationships, there may not be confidence in the ability to control accident scenarios to below mercury’s IDLH or PAC-III levels for future cleaning initiatives.

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Capability to Recover Plutonium-238 in H-Canyon/HB-Line - 13248

Plutonium-238 is used in Radioisotope Thermoelectric Generators (RTGs) to generate electrical power and in Radioisotope Heater Units (RHUs) to produce heat for electronics and environmental control for deep space missions. The domestic supply of Pu-238 consists of scrap material from previous mission production or material purchased from Russia. Currently, the United States has no significant production scale operational capability to produce and separate new Pu-238 from irradiated neptunium-237 targets. The Department of Energy - Nuclear Energy is currently evaluating and developing plans to reconstitute the United States capability to produce Pu-238 from irradiated Np-237 targets. The Savannah River Site had previously produced and/or processed all the Pu-238 utilized in Radioisotope Thermoelectric Generators (RTGs) for deep space missions up to and including the majority of the plutonium for the Cassini Mission. The previous full production cycle capabilities included: Np- 237 target fabrication, target irradiation, target dissolution and Np-237 and Pu-238 separation and purification, conversion of Np-237 and Pu-238 to oxide, scrap recovery, and Pu-238 encapsulation. The capability and equipment still exist and could be revitalized or put back into service to recover and purify Pu-238/Np-237 or broken General Purpose Heat Source (GPHS) pellets utilizing existing process equipment in HB-Line Scrap Recovery, and H-Canyon Frame Waste Recovery processes. The conversion of Np-237 and Pu-238 to oxide can be performed in the existing HB-Line Phase-2 and Phase- 3 Processes. Dissolution of irradiated Np-237 target material, and separation and purification of Np-237 and Pu-238 product streams would be possible at production rates of ∼2 kg/month of Pu-238 if the existing H-Canyon Frames Process spare equipment were re-installed. Previously, the primary H-Canyon Frames equipment was removed to be replaced: however, the replacement project was stopped. The spare equipment is stored and still available for installation. Out of specification Pu-238 scrap material can be purified and recovered by utilizing the HB-Line Phase- 1 Scrap Recovery Line and the Phase-3 Pu-238 Oxide Conversion Line along with H-Canyon Frame Waste Recovery process. In addition, it also covers and describes utilizing the Phase-2 Np-237 Oxide Conversion Line, in conjunction with the H-Canyon Frames Process to restore the H-Canyon capability to process and recover Np-237 and Pu-238 from irradiated Np-237 targets and address potential synergies with other programs like recovery of Pu-244 and heavy isotopes of curium from other target material. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Prospects for applications of electron beams in processing of gas and oil hydrocarbons

Waste-free processing of oil and oil gases can be based on electron-beam technologies. Their major advantage is an opportunity of controlled manufacturing of a wide range of products with a higher utility value at moderate temperatures and pressures. The work considers certain key aspects of electron beam technologies applied for the chain cracking of heavy crude oil, for the synthesis of premium gasoline from oil gases, and also for the hydrogenation, alkylation, and isomerization of unsaturated oil products. Electronbeam processing of oil can be embodied via compact mobile modules which are applicable for direct usage at distant oil and gas fields. More cost-effective and reliable electron accelerators should be developed to realize the potential of electron-beam technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simulation of cooling and solidification of three-dimensional bulk borosilicate glass. Effect of structural relaxations

The modeling of the viscoelastic stress evolution and specific volume relaxation of a bulky glass cast is presented in this article and is applied to the experimental cooling process of an inactive nuclear waste vitrification process. The concerned borosilicate glass is solidified and cooled down to ambient temperature in a stainless steel canister, and the thermomechanical response of the package is simulated. There exists a deviant compression of the liquid core due to the large glass package compared to standard tempered glass plates. The stress load development of the glass cast is finally studied for different thermal load scenarios, where the cooling process parameters or the final cooldown rates were changed, and we found a great influence of the studied cooldown rates on the maximum stress buildup at ambient temperature.

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Feasible conversion of solid waste bauxite tailings into highly crystalline 4A zeolite with valuable application

Highlights: • Concept to convert waste to valuable product is carried out in this study. • An industrially feasible and cost-effective approach was developed and optimized. • Highly crystalline and well-defined zeolite was produced under moderate conditions. • The zeolite derived from the bauxite tailings displayed high ion exchange capacity. • Bauxite tailings have potential application in heavy metal ions adsorbent. - Abstract: Bauxite tailings are a major type of solid wastes generated in the flotation process. The waste by-products caused significant environmental impact. To lessen this hazardous effect from poisonous mine tailings, a feasible and cost-effective solution was conceived and implemented. Our approach focused on reutilization of the bauxite tailings by converting it to 4A zeolite for reuse in diverse applications. Three steps were involved in the bauxite conversion: wet-chemistry, alkali fusion, and crystallization to remove impurities and to prepare porous 4A zeolite. It was found that the cubic 4A zeolite was single phase, in high purity, with high crystallinity and well-defined structure. Importantly, the 4A zeolite displayed maximum calcium ion exchange capacity averaged at 296 mg CaCO{sub 3}/g, comparable to commercially-available zeolite (310 mg CaCO{sub 3}/g) exchange capacity. Base on the optimal synthesis condition, the reaction yield of zeolite 4A from bauxite tailings achieved to about 38.43%, hence, this study will provide a new paradigm for remediation of bauxite tailings, further mitigating the environmental and health care concerns, particularly in the mainland of PR China.

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Characterization of Non-pertechnetate Species Relevant to the Hanford Tank Waste

Among radioactive constituents present in the tank waste stored at the U.S. DOE Hanford Site, technetium-99 (Tc), which is generated from the fission of 235 U and 239 Pu in high yields, presents a unique challenge in that it has a long half-life ( = 292 keV; T1/2 = 2.11105 y) and exists predominately in soluble forms in the liquid supernatant and salt cake fractions of the waste. In the strongly alkaline environments prevalent in most of the tank waste, its dominant chemical form is pertechnetate (TcO 4 - , oxidation state +7). However, attempts to remove Tc from the Hanford tank waste using ion-exchange processes specific to TcO 4 - only met with limited success, particularly when processing tank waste samples containing elevated concentrations of organic complexants. This suggests that a significant fraction of the soluble Tc can be present as low-valent Tc (oxidation state < +7) (non-pertechnetate). The chemical identities of these non-pertechnetate species are poorly understood. Previous analysis of the SY-101 and SY-103 tank waste samples provided strong evidence that non-pertechnetate can be comprised of [fac-Tc(CO) 3 ] + complexes containing Tc in oxidation state +1 (Lukens et al. 2004). During the last three years, our team has expanded this work and demonstrated that high-ionic-strength solutions typifying tank waste supernatants promote oxidative stability of the [fac-Tc(CO) 3 ] + species (Rapko et al. 2013a; 2013b; Levitskaia et al. 2014; Chatterjee et al. 2015). Obtained results also suggest possible stabilization of Tc(VI) and potentially Tc(IV) oxidation states in the high-ionic-strength alkaline matrices particularly in the presence of organic chelators, so that Tc(IV, VI) can serve as important redox intermediates facilitating the reduction of Tc(VII) to Tc(I). Designing strategies for effective Tc management, including separation and immobilization, necessitates understanding the molecular structure of the non-pertechnetate species and their identification in the actual tank waste samples, which would facilitate development of new treatment technologies effective for dissimilar Tc species. The key FY 2016 results are summarized below.

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Remote Handled Hot Cell Facility and Other Research Transuranic Waste (Debris)

This acceptable knowledge (AK) Summary Report has been prepared for the Central Characterization Program (CCP) for remote-handled (RH) transuranic (TRU) waste generated and managed by Sandia National Laboratories/New Mexico (SNL/NM) in Albuquerque, New Mexico. The waste described in this report was predominately generated in the SNL/NM Hot Cell Facility (HCF) during the removal and packaging of experimental material and decontamination operations in Building 6580 at Technical Area (TA)-V. The waste stream also includes a very small amount of waste (estimated at less than 1 gram of fuel similar to that used for research at the HCF) originating from classified research at TA-I. In addition, the waste also includes secondary waste termed by SNL/NM as process generated waste (PGW), created during repackaging operations for this waste at the Auxiliary Hot Cell Facility (AHCF). The waste has been stored at the Sandia Pulsed Reactor (SPR) Dense Pack Storage Facility within TA-V or the Manzano Bunkers located at Manzano Base within Kirtland Air Force Base. All of the waste is being repackaged at the AHCF. This report was prepared in accordance with CCP-TP-005, CCP Acceptable Knowledge Documentation (Reference 1), to implement the AK requirements of DOE/WIPP-02-3214, Remote-Handled TRU Waste Characterization Program Implementation Plan (WCPIP) (Reference 2); Waste Isolation Pilot Plant Hazardous Waste Facility Permit, Waste Analysis Plan (WIPP-WAP) (Reference 3); and DOE/WIPP-02-3122, Transuranic Waste Acceptance Criteria for the Waste Isolation Pilot Plant (WIPP-WAC) (Reference 4).

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Nuclear Safety [Vol. 37, No. 2, April-June 1996]

Nuclear Safety is a journal that covers significant issues in the field of nuclear safety. Its primary scope is safety in the design, construction, operation, and decommissioning of nuclear power reactors worldwide and the research and analysis activities that promote this goal, but it also encompasses the safety aspects of the entire nuclear fuel cycle, including fuel fabrication, spent-fuel processing and handling, and nuclear waste disposal, the handling of fissionable materials and radioisotopes, and the environmental effects of all these activities. Table of Contents for this issue follows. GENERAL SAFETY CONSIDERATIONS: 97 The Nuclear Community and the Public: Cognitive and Cultural Influences on Thinking About Nuclear Risk, M. A. Meyer; 109 Twenty-Third Water Reactor Safety Information Meeting, D. A. Copinger; ACCIDENT ANALYSIS: 126 Analysis of a PWR LBLOCA Without SCRAM, Trevor N. Tyler, Rafael Macian-Juan and John H. Mahaffy; DESIGN FEATURES: 139 Vulnerability of Multiple-Barrier Systems, N. C. Lind; ENVIRONMENTAL EFFECTS: 149 A Study of Wet Catalytic Oxidation of Radioactive Spent Ion Exchange Resin by Hydrogen Peroxide, Xingchao Jian, Tianbao Wu, and Guichun Yun; 157 A Comparison Study and Resolution of Differences Between Emergency Response and Safety Analysis Codes Used at the Savannah River Site, A. A. Simpkins; OPERATING EXPERIENCES: 164 Reactor Shutdown Experience, Compiled by J. W. Cletcher; RECENT DEVELOPMENTS: 167 Reports, Standards, and Safety Guides, D. S. Queener; 172 Proposed Rule Changes as of Dec. 31,1995; ANNOUNCEMENTS: 178 American Nuclear Society 1997 Annual Meeting; 178 American Nuclear Society Nuclear Criticality and Safety Division Topical Meeting; 176 The Authors.

05 NUCLEAR FUELS↗

Technologies for ECLSS Evolution

Viewgraphs and discussion on technologies for Environmental Control and Life Support System (ECLSS) evolution are presented. Topics covered include: atmosphere revitalization including CO2 removal, CO2 reduction, O2 generation, and trace contaminant control; water recovery and management including urine processing, hygiene water processing, and potable water processing; and waste management. ECLSS technology schematics, process diagrams, and fluid interfaces are included.

Diamant, Bryce L.↗

Advanced collapsible tank for liquid containment

Tanks for bulk liquid containment will be required to support advanced planetary exploration programs. Potential applications include storage of potable, process, and waste water, and fuels and process chemicals. The launch mass and volume penalties inherent in rigid tanks suggest that collapsible tanks may be more efficient. Collapsible tanks are made of lightweight flexible material and can be folded compactly for storage and transport. Although collapsible tanks for terrestrial use are widely available, a new design was developed that has significantly less mass and bulk than existing models. Modelled after the shape of a sessible drop, this design features a dual membrane with a nearly uniform stress distribution and a low surface-to-volume ratio. It can be adapted to store a variety of liquids in nearly any environment with constant acceleration field. Three models of 10L, 50L, and 378L capacity have been constructed and tested. The 378L (100 gallon) model weighed less than 10 percent of a commercially available collapsible tank of equivalent capacity, and required less than 20 percent of the storage space when folded for transport.

Flanagan, David T.↗