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At least 829 records · Page 46

A two-stage strategy for upcycling chlorine-contaminated plastic waste

Abstract Chemical upcycling of polyolefin plastic waste to lubricant, wax and fuel-range hydrocarbons over metal-based catalysts is a crucial technological solution to the enormous environmental threat posed by plastic waste. However, currently available methods are incompatible with chlorine-contaminated feedstocks. Here we report a two-stage strategy for upcycling chlorine-contaminated polypropylene. First, magnesia–alumina mixed oxide at 30 bar H 2 and 250 °C serves as a chlorine trap by rapidly forming solid chloride, resulting in nearly complete chlorine extraction from the polyolefin melt. This enables the upcycling of plastic waste with up to 10% polyvinyl chloride content to lubricants over ruthenium-based catalysts, in the second stage. The strategy is also applicable to chlorinated aromatics and alkanes. The proposed strategy renders hydrocracking and hydrogenolysis catalysts less sensitive to the chlorine impurities in feedstocks while eliminating HCl emissions and chlorine contamination in products. It could incentivize further progress in plastics upcycling.

Environmental Sciences & Ecology↗

Metal oxide supported Ni-impregnated bifunctional catalysts for controlling char formation and maximizing energy recovery during catalytic hydrothermal liquefaction of food waste

Nickel (Ni)-impregnated metal oxide catalysts, Ni/CeZrO x , Ni/ZrO 2 , and Ni/CeO 2 , were investigated to maximize energy recovery and reduce char yield during catalytic hydrothermal liquefaction (CHTL) of food waste. Yields of char, biocrude, water soluble products, and gas were measured at 300 °C and 1 hour for both the parent oxides (CeZrO x , ZrO 2 , and CeO 2 ) and the Ni-impregnated versions. Using Ni-based catalysts reduced the carbon-weighted char yield from 16–24% to <10% and decreased the energy recovery of char from 39–47% to <21%, as compared with control tests. In particular, using Ni/ZrO 2 resulted in the greatest biocrude yield, greatest reduction of char yield, and greatest energy recovered as biocrude (39.2%). After factoring in all forms of usable energy produced from food waste, the total energy recovery obtained for the catalysts studied here was >60%. Ni/ZrO 2 and Ni/CeO 2 show the greatest potential for controlling char growth and maximizing energy recovered from food waste. The crystalline structures of all three oxides were hydrothermally stable. Catalyst reuse tests indicate that the biocrude and char yields remained the same for the first and second use (within uncertainty) and that the catalyst retains its initial crystallinity and 93% of its initial Ni content. Molecular composition of biocrudes analyzed by the state-of-the-art analytical platforms (including GC-MS, GC × GC, FT-ICR MS, and 1H NMR) revealed minor differences in the chemical constituents of biocrudes obtained using different catalysts and provided some insight regarding reaction mechanism.

09 BIOMASS FUELS↗

Conversion of plastic waste into high-value lubricants: techno-economic analysis and life cycle assessment

Given the low recycling rate of plastic waste in the United States due to low economic incentives, it is of great interest to develop a technology to upgrade plastic waste with favorable economics. Plastic upcycling to valuable chemicals could ensure a circular economy for plastics and reduce the environmental burden caused by their end use cycle and disposal. A conceptual facility to convert 250 metric ton (MT) per day of plastic waste was modeled; the main product was a high-quality liquid (HQL) with a similar performance to polyalphaolefin (PAO) lubricants. The modeled process had a lubricant yield of up to 90% based on the experimental results at the laboratory scale. Techno-economic analysis (TEA) and life cycle assessment (LCA) were also performed to evaluate the process economics and its environmental impact. By using a mixture of colored and natural high-density polyethylene (HDPE), the production cost was in the range of 0.6–1.98 dollars per kg of lubricant, depending on the operating conditions. The life cycle emissions were in the range of 0.48–1.2 kg CO 2e kg Lub -1 showing, for the best case scenario, a 52% reduction relative to the emissions for petroleum lubricants, and a 74% reduction relative to the emissions for PAO lubricants. Finally, the impacts of the lubricant yield, the catalyst amount, and reaction time were evaluated, and their effect on the final production cost was discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Economic evaluation of infrastructures for thermochemical upcycling of post-consumer plastic waste

Thermochemical technologies, such as pyrolysis, offer a potentially scalable pathway for upcycling diverse types of plastic waste (PW) into value-added chemicals. However, deploying these technologies in waste management infrastructures is not straightforward because such systems involve a wide range of interdependent stakeholders, processing facilities, and products. In this work, we present a holistic optimization framework that integrates value-chain analysis, techno-economic analysis, and life-cycle analysis for investigating the economic viability and environmental benefits of upcycling infrastructures that collect, sort, clean, and process post-consumer PW for producing virgin polymer resins. The framework is applied to a case study in the upper Midwest region of the US. Our analysis reveals that the infrastructures are economically viable and could activate a regional circular economy that generates over 1 billion USD in annual profit. Moreover, our analysis reveals that this economy can reduce the carbon footprint of PW incineration by half. Our framework also determines the inherent values of post-consumer PW and of derived products such as plastic bales and pyrolysis oil; we find that, in these infrastructures, PW becomes a highly valuable feedstock with a market value of 500 USD per tonne. Here, we discuss how this market value can generate incentives that foster more effective waste pre-sorting practices by consumers that can help bypass material recycling facilities and increase total system profit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical characterization of microplastic particles formed in airborne waste discharged from sewer pipe repairs

Microplastic particles are of increasing environmental concern due to the widespread uncontrolled degradation of various commercial products made of plastic and their associated waste disposal. Recently, common technology used to repair sewer pipes was reported as one of the emission sources of airborne microplastics in urban areas. This research presents results of the multi-modal comprehensive chemical characterization of the microplastic particles related to waste discharged in the pipe repair process and compares particle composition with the components of uncured resin and cured plastic composite used in the process. Analysis of these materials employs complementary use of surface-enhanced Raman spectroscopy, scanning transmission X-ray spectro-microscopy, single particle mass spectrometry, and direct analysis in real-time high-resolution mass spectrometry. Further, it is shown that the composition of the relatively large (100 μm) microplastic particles resembles components of plastic material used in the process. In contrast, the composition of the smaller (micrometer and sub-micrometer) particles is significantly different, suggesting their formation from unintended polymerization of water-soluble components occurring in drying droplets of the air-discharged waste. In addition, resin material type influences the composition of released microplastic particles. Results are further discussed to guide the detection and advanced characterization of airborne microplastics in future field and laboratory studies pertaining to sewer pipe repair technology.

54 ENVIRONMENTAL SCIENCES↗

Influence of functional additives, fillers, and pigments on thermal and catalytic pyrolysis of polyethylene for waste plastic upcycling

Pyrolysis offers a relatively green and economical method to convert waste plastics into valuable chemicals and fuels without the need for harmful solvents, toxic chemicals, or costly high-pressure reactors. Despite its popularity among chemical upcycling technologies, industrial adoption suffers from feedstock heterogeneity, low-quality products, and catalyst deactivation. Most plastics in our daily lives are formulated with functional additives, fillers, and colorants. These additives remaining in end-of-life waste streams increase feedstock heterogeneity, creating a challenging issue in recycling plastics. Still, the potential impacts of additives on the chemical upcycling of plastics have been poorly understood. In this study, polyethylene compounded with a range of widely used additives (antioxidants, stabilizers, pigments, fillers, slip agents, and flame retardants) was subjected to both thermal pyrolysis and catalytic pyrolysis in different catalyst-to-feedstock contact modes. It showed that many inorganic additives, such as talc, kaolin, CaCO 3 , TiO 2 , carbon black, and zinc stearate, facilitated polymer decomposition during pyrolysis, increasing light hydrocarbons while also promoting aromatic and carbon residue formation. Conversely, antioxidants and stabilizers inhibited depolymerization, favoring heavier hydrocarbons. During catalytic pyrolysis with HZSM-5 zeolite, additives strongly enhanced aromatic and catalytic coke formation, especially when there was direct contact between plastics and catalysts. Although certain additives seem beneficial in the short term by promoting polymer cracking and improving the selectivity of aromatics, the transport of the additives and their degradation products and increased carbon coking can contaminate products, deactivate or modify catalysts, and foul reactors. These findings address a critical knowledge gap in effectively converting waste plastics via a greener route.

42 ENGINEERING↗

Solvent-mediated contaminant removal from plastic waste using thermodynamic modeling

Plastics recycling is hindered by the compositional complexity of plastic waste, which can include numerous polymer components as well as low concentrations of additives and non-intentionally added substances. These latter small-molecule species, which we collectively refer to as contaminants, can harm human health and will build up in recycled plastic causing environmental and downstream processing challenges if not removed. In this work, we present molecular modeling approaches using the COnductor-like Screening MOdel for Real Solvents (COSMO-RS) to guide the selection of solvents that are capable of removing targeted contaminants from plastic waste. By considering the thermodynamic partitioning of contaminant species between a solvent phase and polymer phase, we identify guidelines for solvent selection to promote either the low-temperature extraction of contaminants from plastic waste or the removal of contaminants as part of a dissolution-based plastics recycling process. We present four case studies to illustrate the application of the computational approach to the removal of brominated flame retardants, phthalates, and selected perfluoroalkyl substances, and compare to both literature and newly collected experimental data to illustrate model prediction accuracy. Furthermore, the case studies highlight the capability of the modeling approach to help design recycling processes that explicitly account for contaminant removal, thereby increasing product purity during dissolution-based recycling or facilitating chemical recycling of contaminant-free plastics.

Zhou, Panzheng [University of, Wisconsin, Madison,↗

Developing a Process for Collaboration-Based Siting of a Federal Consolidated Interim Storage Facility in the United States: Learning from Communities Living with Legacy Waste

In June of 2023, the U.S. Department of Energy (DOE), Office of Nuclear Energy (NE) announced the selection of its Collaboration-Based Siting (CBS) Consortia, a group of 12 awardees, including the Consortium for Risk Evaluation with Stakeholder Participation (CRESP) (led by Vanderbilt University) to assist DOE-NE with the development of its process for siting a federal consolidated interim storage facility (FCISF) for spent nuclear fuel (SNF) storage. At this time, DOE NE is not soliciting interested host communities, rather the CBS Consortia are tasked with in-depth engagement, mutual learning, and capacity building to provide DOE NE with feedback on the CBS process. CRESP’s objective is to engage communities in two regions (the Pacific Northwest and the Southeast) with sites currently storing defense- and research-related SNF to foster learning concerning the best and worst practices in community participation in risk-informed decision making. This includes learning from existing structures for public input in radioactive waste management decision making [e.g. citizen advisory boards (CABs)] and other local parties about how to build and sustain trust among the parties. CRESP has been working to engage stakeholders and Tribes surrounding two DOE sites historically differing in receptiveness to engaging with DOE and trusting in DOE to accomplish its missions. CRESP’s approach to date has consisted of (1) engaging voluntarily members and former members of the DOE Office of Environmental Management’s CABs to develop a mutual understanding of their perspectives, values, and experiences related to risk and participatory decision making; (2) engaging members of those communities that would likely be part of any radioactive waste management discussions and who may provide valuable feedback for the development of the CBS process; and in the longer term, (3) engaging communities to foster knowledge sharing on understanding and definitions of risk and how risk is factored into community decision making. Our emphasis is to identify opportunities for improving risk communication frameworks, strategies, and decision making. The selection of a future FCISF site is likely to result in the creation of a structure similar to a CAB composed of members of the local community. We anticipate that these insights can help DOE NE learn from existing participatory risk communication structures in place at sites storing defenseor research-related SNF to understand best practices for fostering enduring and participatory relationships with future CABs. Within this paper, we (1) describe CRESP’s overall approach to assisting DOE NE with maturing the CBS process; (2) present a summary of preliminary phase 1 project results, including the development of a body of knowledge (describing available resources to support community engagement, risk communica tion, and participatory decision making) and community ecosystem information (leveraging demographic, social, economic, and environmental attribute mapping and advanced sentiment analysis of social media data); and (3) based on these results, provide observations for future research opportunities to support the development of CBS processes for radioactive waste management facilities, generally.

collaboration-based siting↗

Review of Ion Exchange Technologies for Cesium Removal from Caustic Tank Waste

This article reviews the historical uses of and current research into ion exchange for the removal of cesium (Cs) from defense-related nuclear waste streams. Emphasis is placed on key attributes of the two current leading ion exchangers for Cs removal: spherical resorcinol-formaldehyde, an elutable organic resin, and crystalline silicotitanate, a non-elutable crystalline solid. An understanding of the successes, issues, and limitations of past ion exchange experience may be helpful in better understanding current ion exchanger use. Emphasis is placed on Cs capacity, exchange kinetics, stability, and column hydrodynamics for processing alkaline wastes as well as the final waste forms of the ion exchangers.

Fiskum, Sandra K.↗

Glass-contact refractory of the nuclear waste vitrification melters in the United States: a review of corrosion data and melter life

The performance of the refractory lining in glass melters used for nuclear waste vitrification is critical to the melter reliability for long-term continuous operation. Monofrax® K-3, a high Cr 2 O 3 fused cast refractory material, has been widely used to build the liners of nuclear waste glass melters in the United States. Corrosion behaviour of Monofrax® K-3 refractory has been evaluated based on crucible-scale testing, inspection of the refractory components following scaled melter testing, and inspections of the Defense Waste Processing Facility (DWPF) melter refractory after service. The literature generally consists of empirical models based on short-term testing to describe refractory corrosion dependence on glass composition. Corrosion data from tests with longer testing times, at various temperatures, in the presence of molten salts, and with different redox reactions in the plenum atmosphere exist, may be insufficient to provide accurate refractory service life estimates. Additionally, the corrosion data collected under actual and scaled melter operating conditions are limited. Recommendations to achieve more direct correlation between the laboratory refractory corrosion data predictions and the observed melter service life are discussed to allow for more accurate predictions of the useful life of melter refractory linings.

Jin, Tongan↗

Effect of water vapor and thermal history on nuclear waste feed conversion to glass

Water affects the glass melting process by interacting with the foam layer at the glass melt surface and by influencing the batch conversion reactions. Water vapor from the nuclear waste slurry feed maintains a high water vapor pressure in the melter atmosphere. To investigate to what extent water vapor affects the vitrification of nuclear waste in joule-heated, cold-top melters, a series of feed expansion experiments were performed under humid and dry atmospheres using samples of low-activity waste (LAW) melter feed simulants. Melting of feed pellets in the presence of water vapor slightly decreased the temperature of primary foam onset, but did not significantly affect the feed volume expansion by foaming or the foam-collapse temperature. Sets of feed expansion experiments and evolved gas analyses were also performed to check the effect of thermal history on LAW feed samples tested as direct slurry, loose powder, and slow- and fast-dried pellets.

Marcial, Jose↗

A comparison of ceramic and carbon-based reductants for vitrification of low-activity waste

Sucrose is the current baseline additive at the Hanford Waste Treatment and Immobilization Plant in Washington, USA to control foaming during waste feed to glass transitions and the redox state of the glass melt. Alternative reductants are being investigated to alleviate strain on effluent treatment from toxic acetonitrile production from incomplete combustion of sucrose. This study evaluates ceramic additive options including B4C, B6Si, SiC and VB2 in simulated low-activity waste feed, as well as coke dust, probing the feed volume expansion during melting as well as the gas evolution. All alternative reductant options examined significantly reduced acetonitrile production, however there was variability in their effectiveness as foam-reducing agents. VB2 and coke at the appropriate ratios were similarly effective as sucrose in controlling both foam volume and glass redox state, but with considerably less acetonitrile production. B4C, B6Si and SiC showed more promising foam control and very little acetonitrile production, however all of the final glasses were over reduced, i.e., Fe2+/FeT = 0.5. These alternative reductant studies provide operational flexibility to the operation of the vitrification plant, as well as options for alternative raw materials in industrial glass melting.

Rigby, Jessica C. (ORCID:0000000235719977)↗

Corrosion behavior of Monofrax K-3 refractory in borosilicate-based model low activity waste glass melts

Owing to its good chemical and thermal durabilities at high temperatures, Monofrax K-3 refractory is widely used in nuclear waste vitrification as a lining material in melting vessels. However, the corrosion of K-3 refractory during the vitrification of nuclear waste is a serious problem because it affects the melter's safety, performance, and lifetime. Therefore, in the present study, we have focused on unearthing the impact of glass network formers, such as SiO 2 , B 2 O 3 , and Al 2 O 3 , in a model nuclear waste glass composition on the corrosion of Monofrax K-3 refractory. The corrosion tests have been performed per ASTM C621 at 1150°C for 5 days. The dimensional measurements on corroded K-3 refractory suggest that Al 2 O 3 and SiO 2 tend to reduce the refractory corrosion (neck loss), with the effect of Al 2 O 3 being significant. A corroded region on the K-3 refractory at the melt–refractory interface is observed. The corrosion occurs via a coupling of the melt infiltration induced by a capillary effect and the dissolution of Al, Mg, and Fe components from K-3 into the melt through chemical reactions. A Cr-rich layer is retained on the glass contact surface of the corroded K-3 refractory.

36 MATERIALS SCIENCE↗

Soil Desiccation Treatability Testing at BC Waste Disposal Cribs

During Hanford’s production period, low-level waste products generated from chemical processing of uranium fuel rods were discharged directly to the ground through a system of cribs and trenches located in the 200-BC-1 Operable Unit (OU). The site consists of 6 cribs and 20 trenches that received more than 117,000 m3 of radioactive liquid waste discharged to the soil. These unlined infiltration galleries held volumes of liquid waste while it seeped into the ground, with the understanding that the 100 m (330 ft) thick vadose zone in the area would effectively capture the effluent and prevent groundwater impacts. A conceptual model showing the operation of cribs and trenches is shown in Figure 1. Data show effluent from the 26 cribs and trenches containing about 410 curies of Technetium-99 (Tc-99) is primarily located between 30 m and 70 m (98 ft and 230 ft) depth (Corbin et al., 2005; Ward et al., 2004). Despite no evidence indicating that the contamination has reached the groundwater at BC cribs and trenches, the mobility of Tc-99 had been demonstrated in laboratory tests and was recognized as a threat to groundwater at the site. Using data from numerical models, laboratory analyses, field investigations, and information on historical discharges, the EPA and Ecology identified Tc-99 and U contamination of the vadose zone as a remediation priority. The U.S. DOE was notified by EPA and Ecology regarding risks associated with Tc-99 contamination in a letter requesting development of a strategy for improved methods to understand the nature and extent of vadose zone contamination, specifically Tc-99, and to develop remedial options for addressing such contamination. To develop the appropriate technology for characterizing, remediating, and monitoring the deep vadose zone Tc-99 contamination, the U.S. DOE worked with the EPA and Ecology to create a Treatability Test Plan under a Remedial Investigation/Feasibility Study (RI/FS) for the Hanford 200 Areas. Under this RI/FS, it was determined that a treatability test for soil desiccation should be carried out as it was identified as a promising in-situ treatment technology for mitigating risks posed by Tc-99 contamination to the groundwater table. The BC Cribs and Trenches site was identified as a representative site for Tc-99 and U contamination and selected for the soil desiccation treatability test. In this chapter, we summarize the overlying regulatory framework of RI/FS and treatability tests and illustrate how development and experimentation supported the evaluation of selected remedies. We briefly discuss the RI/FS for the 200 Areas of the Hanford Site and focus on the soil desiccation treatability testing performed at the BC cribs and trenches site under the Deep Vadose Zone Treatability Test Plan for the Hanford Central Plateau (DVZ-TT). The DVZ-TT is one component of the remedial investigation/feasibility study for the Hanford 200 Areas and represents the underlying regulatory framework that drives site operations towards records of decision and site closure.

Mangel, Adam R.↗

Investigation into Na and Cs activity coefficients in high salt solutions to support Cs removal in Hanford tank waste

The treatment of Hanford tank waste is one of the most technically challenging environmental cleanup activities for the U.S. Department of Energy to date. To expedite the processing of liquid waste stored in underground tanks in southeastern Washington state, it is necessary to remove the significant dose contributor, 137 Cs. Toward this effort, ion exchange with crystalline silicotitanate (CST) has been employed as part of the Tank Side Cesium Removal system. The model used to predict Cs exchange onto CST was developed using activity coefficients calculated from the Bromley equation. A series of batch contact tests that varied in [Na] were conducted to look at the impact of Na concentration on Cs distribution. Experimental distribution ratios ( K d ) were compared to the distribution ratios predicted using three different activity coefficient models: (1) commercially available HSC software, (2) the Bromley equation, and (3) a simplified approach adapted from Marcos-Arroyo et al. Ultimately, the Bromley method underpredicted the effect of ionic strength on the Na activity coefficient ( γ Na+ ), HSC overestimated the impact of ionic strength on the expected performance due to the Cs activity coefficient ( γ Cs+ ), but the simplified approach predicted the experimental K d values quite well in a binary matrix. In conclusion, expansion of this approach in complex matrices is necessary for application to Hanford tank waste.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Recycling Isotopically Enriched Mo from the RadioGenix Waste Stream

NorthStar’s RadioGenix generator utilizes an aqueous biphasic extraction chromatography column to separate Tc from low-specific-activity 99 Mo. During this separation process, a fraction of the source Mo material can be found in the waste. This is not of concern when natural Mo targets are used. However, the introduction of isotopically enriched 98 Mo for neutron capture or 100 Mo for accelerator-based production requires recovery of this valuable enriched Mo material. The generator waste is absorbed and solidified in a superabsorbent hydrogel polymer. In this contribution, we report results from our small-scale experimental study on development of a separation process for recovery of molybdenum from the polymeric gel waste using common chemicals and simple chemical techniques. Our investigation confirms that the acidic deswelling of the alkaline hydrogel with concentrated hydrochloric acid converts the occluded molybdate to a neutral molybdenyl dichloride species that is freely released from the gel. Mo can then be concentrated on a commercial tri-n-butyl phosphate resin, eluted with ammonium hydroxide, and crystallized as ammonium heptamolybdate for conversion back to Mo metal. Typical Mo recoveries are 90-95%.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Engineered Barrier System R&D and International Collaborations – LANL (FY20): Spent Fuel and Waste Disposition

The United States Department of Energy’s Spent Fuel and Waste Disposition (SFWD) program is investigating the design and safety function of generic nuclear geologic repositories in a variety of geologic settings (salt, argillite, and crystalline rock). Different configurations and loadings of spent nuclear fuel and waste within disposal canisters are also being investigated, some of which have the potential to generate repository temperatures higher than previously considered (i.e., temperatures >100ºC) by foreign and domestic concepts. This report expands on engineered barrier material stability in a high temperature crystalline rock repository through high temperature hydrothermal experiments. Experiments were designed to develop engineered barrier system (EBS) concepts in a hightemperature crystalline environment in 1) bentonite-Grimsel Granodiorite interactions, 2) bentonite-cement reactions, and 3) interaction between waste canister materials and bentonite. Experiment results are applied to understanding long-term repository performance in terms of radionuclide isolation. One hydrothermal experiment was completed in the rocking autoclaves at LANL in FY-20: IEBS-6 (Grimsel Granodiorite + Wyoming bentonite + cured ordinary Portland cement + Grimsel Granodiorite synthetic groundwater, 250ºC/150 bar, 8 weeks). Several other experiments were planned but were delayed due to the COVID-19 pause in laboratory work. In addition, some characterization of the reaction products of experiments conducted in FY-20 was prevented by COVID-19. Mineral phase chemistry was not measured via electron microprobe analyses for IEBS-6. Quantitative X-ray diffraction results from IEBS-6 and HBT-1 were not completed. The missing analyses and discussion of the results will be included in next year’s report. New characterization that was completed includes scanning electron microscopy of reaction products from IEBS-6, quantitative X-ray diffraction results are presented from IEBS-1 through IBES-5, preliminary scanning electron microscope images and chemical analyses for IEBS-6, X-ray diffraction of the clay fraction from all experiments, measurement/imaging of mineral growth on the surface of steel coupons. Major observations pertaining to bentonite stability in a Grimsel Granodiorite environment include the stability of Na-montmorillonite at 250°C, the formation of trace CSH phases, and the formation of bentonite colloids on experiment cooling. The addition of a cured chip of Portland cement to the bentonite-Grimsel system results in slightly higher pH values and the formation of diverse secondary mineral phases that were not observed in the previous experiments (e.g., analcime, garronite, CSH phases). The new characterization efforts related to the interaction of stainless-steel coupons and bentonite clay focused on thickness and mineralogy of phases that formed at the steel surface. In Wyoming bentonite + Grimsel Granodiorite systems, newly formed minerals at the bentonitesteel coupon interface included alteration of the outermost steel edge to Fe,Cr-oxide phases, followed by Fe-rich phyllosilicates (Fe-saponite, chlorite) and interbedded Fe,Cr,Ni-sulfide phases (pentlandite). Hydrothermal experiments were completed to assess uranium-carbonate complexation at conditions relevant to high-temperature disposal. Autoclave solubility experiments were conducted at 150 to 250ºC with a range of carbonate and uranium concentrations. The experiment results were characterized via situ UV-Visible spectroscopy and synchrotron-based in situ XAS techniques. Results show a significant decrease in the stability of uranyl-carbonate complexes at temperatures above 100ºC along with the precipitation of uranium oxides. Further, at T > 200ºC, results show that uranyl-hydroxyl complexes control solubility of uranium instead of the previously predicted uranyl-carbonate species. These results are significant for understanding the mobility of uranium in the EBS, which will likely contain carbonate-rich fluids. International research efforts focused on three main areas: 1) participation in international conferences, 2) building collaborations with foreign repository programs, and 3) the initiation of an experimental program to complement the full-scale HotBENT test at the Grimsel test site. This experiment included Wyoming bentonite + low carbon steel + Grimsel Granodiorite synthetic groundwater and was run at the planned maximum temperature of the HotBENT test (200°C). Complete characterization of reaction products was hindered by disruptions to laboratory work but will be reported in the next FY. The experimental results obtained in FY-20 continue to document the wide-ranging effects of bulk composition and pressure-temperature conditions in the mineralogical and geochemical evolution of a high-temperature repository environment. Concepts developed will be used to inform models of long-term material stability in a generic crystalline rock-hosted repository.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Updated Medical Waste Management Plans and Emergency Action Plans for the Lawrence Livermore National Laboratory Main Site

Attached are the updated Medical Waste Management Plans and Emergency Action Plans for Lawrence Livermore National Laboratory’s (LLNL) Biosafety Level 2 (BSL-2) facilities and Biosafety Level 3 (BSL-3) facility. A redline version of each document has also been provided. Minor changes such as facility personnel, contact information, and titles for those that support onsite Biosafety Labs at LLNL have been made to the document. It should be noted that the most recent versions of the Medical Waste Large Quantity Generator Registration Application Form and Medical Waste Management Plan were incorporated and sourced from the Alameda County Department of Environmental Health website.

54 ENVIRONMENTAL SCIENCES↗