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At least 289 records · Page 16

The Utility of Waste Tank Historical Reviews in Bulk Waste Removal Operations at the Savannah River Site – 25271

SRMC is actively working to remove, treat, and dispose radioactive waste generated by the separation facilities at SRS since their initial operations in the 1950s. The separation facilities at SRS have produced nuclear materials for a variety of purposes, particularly national defense, and continue to support the disposition of spent fuel through the Accelerated Basin Deinventory program. In almost 70 years of operation, nearly 625,000 m3 (165 million gallons) of radioactive waste have been generated and transferred to the tank farm facilities at SRS [1]. As a result of volume reduction (e.g., evaporation) and waste solidification (e.g., vitrification), approximately 127,000 m3 (33.5 million gallons) of material remain as of June 30, 2024 [2]. This liquid waste has since been stored in 51 large underground waste tanks present on the site. These waste tanks may contain up to 4,921 m3 (1.3 million gallons) of radioactive waste each in the form of saltcake or sludge. SRMC’s contract is to treat and dispose of this waste, clean the tanks, and operationally close them. To date, 8 of the 51 waste tanks have been operationally closed. Waste retrieval and tank closure activities are ongoing in an additional 17 tanks through either operations in the field or in design [3].

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Understanding the efficacy of concentrated interstitial carbon in enhancing the pitting corrosion resistance of stainless steel

By introducing a high fraction of interstitial carbon through low temperature carburization, the pitting corrosion resistance of austenitic stainless steel can be significantly improved. Previous work attributed this to strengthening of the passive film by carbon. Here, however, we present a paradigm shift by showing that carbon actually weakens the passive film but strengthens the bonding within the alloy by forming localized (covalent) bonds with the metal atoms (Fe, Cr, Ni). Accordingly, the enhancement in pitting resistance is a result of carbon reducing the metal dissolution rate in a local pit environment by many orders of magnitude, which extremely decreases the growth stability of a pit and prevents it from transitioning into stable growth. Electronic structure calculations confirm that carbon bonds to the metal atoms and that the metal–carbon bonds are 1.4 to 2.0 times stronger than the metal–metal bonds. These results suggest a new strategy for the design of corrosion resistant alloys, namely surface engineering by infusion of concentrated interstitials that form strong bonds with the matrix atoms.

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High-Temperature Thermodynamics of Cerium Silicates, A-Ce 2 Si 2 O 7 , and Ce 4.67 (SiO 4 ) 3 O

Lanthanide disilicates and oxyapatites have potential roles in high temperature applications as thermal (TBC) and environmental barrier coatings (EBC), or possible alteration phases in geological nuclear waste repositories. However, those Ce 3+ -bearing silicates have only been limitedly studied. In this work, we performed detailed structural and thermodynamic investigations on A-Ce 2 Si 2 O 7 (tetragonal, P4 1 ) and Ce 4.67 (SiO 4 ) 3 O (hexagonal, P6 3 /m). The high temperature structural behaviors and coefficients of thermal expansion were determined by in situ high temperature synchrotron X-ray diffraction (HT-XRD) implemented with Rietveld analysis and thermogravimetric analysis coupled with differential scanning calorimetry (TGA-DSC). A-Ce 2 Si 2 O 7 was found to be stable in N 2 and air up to ~1483 K with anisotropic thermal expansion along the a and c axes (α a = 12.3 × 10 -6 K -1 and α c = 12.4 × 10 -6 K -1 ). Ce 4.67 (SiO 4 ) 3 O had a slow partial oxidation between 533 K and 873 K to a new nonstoichiometric phase Ce 3+ 1.67- xCe4 + x Ce 3+ 3 (SiO 4 ) 3 O 1+0.5x , followed by a thermal decomposition to CeO 2 and SiO 2 at ~1000 K in air. By using high temperature oxide melt solution calorimetry at 973 K with lead borate as the solvent, the standard enthalpy of formation was determined for A-Ce 2 Si 2 O 7 (-3825.1 ± 6.0 kJ/mol) and Ce 4.67 (SiO 4 ) 3 O (-7391.3 ± 9.5 kJ/mol). Finally, these thermodynamic parameters were compared with those of CeO 2 , CeSiO 4 , and other silicate oxyapatites for examining their chemical stability in high temperature environments relevant for aeronautical applications, mineral formation, and nuclear fuel cycle.

36 MATERIALS SCIENCE↗

Organic Evaporation, Oxidation, and Hydrolysis Testing in Support of Hanford Sample-and-Send

The Hanford site has approximately 56 million gallons of radioactive mixed waste stored in 156 unretrieved underground storage tanks. The Hanford Waste Treatment and Immobilization Plant (WTP) is being built to treat and immobilize the tank waste. The baseline method for immobilization of Low Activity Waste (LAW) through the WTP is vitrification, but additional immobilization capacity is needed to supplement the initial LAW melters. An alternative cementitious waste form is being investigated for that future immobilization method. However, one impediment to a cementitious waste form is the presence of Land Disposal Restricted (LDR) organic chemicals in tank waste, which are regulated on a concentration-based standard in the final waste form. Hence, if the quantity of organics in LAW is high enough, they must be destroyed or removed to make a waste form compatible with disposal in a mixed low level waste landfill. This work evaluates potential avenues for treatment of LDR organics to eliminate the impediment and permit possible use of a cementitious waste form.

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Colorimetric Detection and Surface Decontamination of Metal Ions by Using Strippable Polymers - 20024

Strippable coating is a low cost and efficient decontamination method far more compatible for the cleaning of surfaces. This method allows contaminant entrapment and removal from different types of surfaces and also characterized by low-secondary waste generation after decontamination. The present work deals with the elaboration and testing of a new composition of Polyvinyl alcohol (PVA) aqueous solutions utilize the TTA (Thenoyl trifluoroacetone) ligand, employed as a strippable coating for the removal of metal ions e.g., UO{sub 2}{sup +2}, Ni{sup +2}, Cu{sup +2}, Fe{sup +3}, V{sup +5}, Eu{sup +3} and Cs{sup +} from 'contaminated' surfaces. The study aims at developing contaminant-sensing and decontaminating coatings for the detection and removal of metal ions from non porous surfaces. This 'smart' coating is shown to exhibit a clear contaminant dependent response in the form of color variation, and a detection sensitivity less than 0.5 μg per cm{sup 2}. (authors)

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Studies on the Vitrification Potential of High Risk Spent Nuclear Fuels

This research explored vitrification of U-Zr nuclear fuel that exhibits an explosion hazard when processed by common nitric acid dissolution. Glass frits were chosen based on properties that had been previously measured as well as being demonstrated successfully in production at the Defense Waste Process Facility (DWPF). Zirconium and Aluminum metal powders were chosen to represent the spent fuels after literature demonstrated that the potential phase that causes the issue for explosive reaction in the effluent stream is tied to the Zirconium-III phase field. DSC measurements were carried out on various simulants and waste forms to better understand thermal behavior of these materials. Zirconium (Zr) was tested with both nitric acid and the new effluent flowsheet that is under development by the SRNL Chemical Process Control (CPC) group. The nitric acid test did show the expected exothermic behavior as well as how the behavior is affected by particle size of the powders used. In contrast, the effluent samples did not show an exothermic peak. However, the concentration of metal in the samples was orders of magnitude lower than in the nitric acid testing and further testing of the effect of concentration on the exothermicity that could be measured confirmed a dampened signal. Tests were run that included frit, both DWPF Frit 510 and Iron Phosphate frit, exhibiting complex curves that included multiple endothermic and exothermic peaks during heating and cooling. The final crucible samples appear similarly to the bulk glasses pointing to these peaks being a part of the dissolution of the simulant into the base glasses.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Large Volume Airborne Contamination Monitoring To Support Nuclear Processes' Deactivation and Decommissioning

Current D and D operations at Hanford have demonstrated a flaw in the current state of the art capability of defining airborne contamination boundaries - Airborne particulate emissions of Pu-239 from CM2H operations on the Hanford Pu Finishing Plant were detected well beyond areas controlled for airborne Pu, putting numerous workers at risk for radiological assimilations - Current air samplers and CAM systems were surveying insufficient volumes of air to accurately predict where respiratory protection was required - Hanford is located in a high radon environment, making air monitoring for alpha emitting actinides challenging in high alpha radon induced backgrounds. - Inexpensive HEPA based home and industrial air purifiers filter significantly higher volumes of air than commercially available continuous-air monitoring (CAM) systems. - Inexpensive models capable of filtered air volumes exceeding 1000 times that of a CAM. - Detector system can be built to detect x-rays generated from actinide decay. - Branching ratios of x-rays are 4 orders of magnitude more intense from Plutonium decay than its gamma emissions. - Detector system can be a low resolution systems, as x-ray region of interest is not terribly congested. - Detection systems evaluated will be designed based on slabs of NaI or pixelated NaI or CsI panels. - Simple graphical user interface software will be developed to operate the detection system. - Concept is to deploy some of these air-purifying systems in nonradiological areas around SRNL to confirm radon can be rejected with confidence. - Generate some filters contaminated with plutonium via electroplated Pu or lab generated simulated particles. - then deploy units in known airborne radiological environments to establish systems ability to accurately measure actinide based hot particles Lab analyses will follow up the system analyses to ensure hot particles were correctly identified. Analysis by Scintillation: - Application of scintillation media to the surface of the filters is being explored. - Evaluating slabs of ZnS(Ag), application of powdered ZnS(Cu) and spray on Perkin Elmer Enhance. - Scintillation events would then be digitized with a digital camera and quantified. - Comparing against sensitivity of a PMT or SiPD readout. - Currently evaluating a Thorlabs 8 Megapixel Monochrome Scientific CCD Camera, hermetically sealed cooled package with a wide angle lens. - Wide angle lens allows complete view of HEPA filter from 7 inches away. - Images taken of glow in the dark paint, as well as plutonium-induced fluorescence. - Plutonium was flamed mounted on a 1 inch diameter stainless steel planchet, covered with a layer of mylar and a section of scintillating ZnS obtained from Eljon. - Currently working on reducing signal-to-noise levels to boost sensitivity. - Dark box to hold contaminated or electroplated source covered filters under fabrication. Analysis by x-ray Spectroscopy: - Branching ratios for x-ray emissions from Plutonium isotopes are orders of magnitude more intense than gamma-ray emissions. - The nuclear databases are incomplete on the branching ratios of some of the isotopes. - Evaluating some custom built SrI2 x-ray spectrometers vs a conventional windowed NaI detector. - SrI2 detectors are carbon-composite-windowed 51 mm x 51 mm. - MCNP calculations to establish self absorbance of filter media on 17 keV x-ray. Radon Rejection: - Activated charcoal pre-filter acts as a Radon trap. - Adding a time lapse feature to camera to aid in radon rejection. SRS Plutonium Fuel Form D and D Operations: Currently deploying air sampler to D and D operation of Pu-238 facility at SRS to generate some field samples to analyze.

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Glass production rate in an electric melter: Melting rate correlation and primary foam stability

Waste loading and melting rate are major factors determining the lifecycle of nuclear waste disposal by vitrification in electric melters in which the heat to the cold cap is delivered from the melt pool. One of the crucial parameters that affect the rate of melting is the temperature at which the primary foam collapses at the cold cap bottom. Further, apart from the transient glass-forming melt viscosity, primary foam stability is affected by the shear stress imposed by the flow in the melt pool and the presence of residual solid particles.

36 MATERIALS SCIENCE↗

Separated waste stream immobilization of iodine and off-gas caustic scrubber solution (Final Report)

In this work, the approach was to immobilize the CS solution in a glass-bonded composite of cancrinite/sodalite. The synthesis of ceramic waste forms was accomplished by low-temperature (~90°C) processes developed by the team in the framework of a previous NEUP project. By building on our earlier efforts for iodine waste forms, we minimized the schedule and technical risk while still providing novel process demonstrations for the off-gas waste forms. In the case of AgI-based sorbents, a proof-of-concept stripping process was shown to remove iodine from AgI by converting it to NaI(aq) followed by immobilization of these ions in iodosodalite (ISOD), which could be glass-bonded in the same way as for the CS solution cancrinite/sodalite powders.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

OWL and Waste Form Characteristics (Annual Status Update)

This report represents completion of milestone deliverable M2SF-21SN010309012 “Annual Status Update for OWL and Waste Form Characteristics” that provides an annual update on status of fiscal year (FY 2020) activities for the work package SF-20SN01030901 and is due on January 29, 2021. The Online Waste Library (OWL) has been designed to contain information regarding United States (U.S.) Department of Energy (DOE)-managed (as) high-level waste (DHLW), spent nuclear fuel (SNF), and other wastes that are likely candidates for deep geologic disposal, with links to the current supporting documents for the data (when possible; note that no classified or official-use-only (OUO) data are planned to be included in OWL). There may be up to several hundred different DOE-managed wastes that are likely to require deep geologic disposal. This draft report contains versions of the OWL model architecture for vessel information (Appendix A) and an excerpt from the OWL User’s Guide (Appendix B and SNL 2020), which are for the current OWL Version 2.0 on the Sandia External Collaboration Network (ECN).

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Qualification of Processing Batches for Tank Closure Cesium Removal Through In-Tank Batch Contact Testing - 20470

The Tank Closure Cesium Removal (TCCR) process at the Savannah River Site (SRS) is currently processing waste from Tank 10H, generating decontaminated salt solution that is sent to Tank 11H. Transfers out of Tank 11H are then disposed of on site as a grout wasteform in the SRS Saltstone Processing Facility. This is a full-scale demonstration of the use of Crystalline Silicotitanate (CST) for the decontamination of aqueous nuclear waste supernate. CST primarily removes cesium from the high sodium alkaline feed, but also adsorbs strontium, actinides, and some other trace metals. The TCCR unit is an at-tank set of four ion exchange columns, with two typically being operated in series during waste processing. Tank 10H is serving a dual function as both the salt dissolution tank as well as the feed tank for the TCCR system. Prior to operation of TCCR, Tank 10H must undergo dissolution campaigns, dissolving the salt cake to form an aqueous salt solution (supernate). After each dissolution campaign, the supernate created must be qualified prior to processing through the TCCR system. Qualification includes detailed characterization of the supernate as well as in-tank batch contact tests to determine the equilibrium loading of Cs-137 on the CST ion exchange media (IONSIV{sup TM} R9120-Ba). In support of the in-tank batch contact testing, Savannah River National Laboratory (SRNL) developed a CST sample holder, also referred to as a 'tea-bag', to hold a measured amount (∼0.1 grams) of pretreated CST between stainless steel screens. The tea-bag fits within a standard stainless steel sample vial that has been modified to allow the flow of supernate to the CST. This sample holder is then immersed in the waste tank allowing free contact between the CST beads and the surrounding liquid, at an effectively infinite liquid-to-solid phase ratio. A pair of tea-bags are deployed in the tank for a period of 10 days for each batch, after which the CST is recovered, digested, and analyzed to determine the loading of cesium isotopes on the CST. This result then supports the TCCR column thermal loading limits for processing as part of the TCCR safety basis. This paper will discuss the design and testing of the CST sample holder, as well as results from the first few batches of waste qualified and subsequently processed through the TCCR system. In addition, results from analyses of Tank 11H samples, showing decontamination of the product will be included. (authors)

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Follow-on Report of Analysis of Approaches to Supplemental Treatment of Low-Activity Waste at the Hanford Nuclear Reservation (Vol. I)

The Hanford Site, in southeast Washington State, is preparing to disposition approximately 56,000,000 gallons (56 Mgal) of radioactive and chemically hazardous wastes currently stored in underground tanks at the site. Tank wastes will be divided into a high-activity fraction and a low-activity fraction for subsequent treatment and disposition. A waste processing and treatment facility, the Waste Treatment and Immobilization Plant (WTP), will include the high-level waste (HLW) vitrification facility (WTP HLW Vitrification Facility) for immobilizing the high-activity fraction and a low-activity waste (LAW) vitrification facility (WTP LAW Vitrification Facility) for immobilizing the low-activity fraction. Both facilities will use vitrification technology to immobilize the Hanford tank wastes in a glass waste form. The volume of LAW to be treated and disposed of following waste retrieval and WTP operations will exceed the planned processing capacity of the WTP LAW Vitrification Facility. ORP-11242,-River Protection Project System Plan, estimates a shortfall in LAW treatment capacity of approximately 56 Mgal, approximately 50% of the projected LAW volume. To maintain the planned tank waste processing mission schedule, the U.S. Department of Energy (DOE) will require additional LAW treatment capacity (termed “supplemental LAW”) external to the WTP process. LAW must be solidified by a treatment technology before the waste can be permanently disposed of in an approved DOE on-site disposal facility or a commercial (state or U.S. Nuclear Regulatory Commission [NRC-licensed]) off-site mixed low-level waste disposal facility. A decision on the approach to supplemental LAW treatment, processing, and disposal has not yet been made

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Nanoscopic structure of borosilicate glass with additives for nuclear waste vitrification

In this report we investigated the nanoscopic structure of borosilicate glasses as a host for high-level radioactive liquid waste (HLLW) in the presence of the additives Na 2 O and CaO/ZnO with and without Li 2 O. These additives have been used to lower the glass melting point, suppress the macroscopic phase separation, and increase the chemical durability of glasses. Small-angle neutron scattering was used to elucidate the effect of the additives on the nanoscopic structure along with macro- and atomic-scale observations obtained using neutron imaging and X-ray diffraction, respectively. The borosilicate glass made without Na 2 O formed a microphase-separated structure of SiO 2 - and B 2 O 3 -rich domains approximately 100 nm in size, and the material was homogeneous at length scales up to millimeters. With the addition of increasing amounts of Na 2 O, the domain spacing decreased. Introducing CaO/ZnO additives induced inhomogeneities in the glass, such as void structures several nanometers in size, although the inhomogeneity was suppressed by the coaddition of Li 2 O. These results provide insights into the performance of host glasses for HLLW vitrification. Incorporating HLLW into glasses is likely to cause changes in the nanoscopic structure of host glasses similar to those revealed here.

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Saltstone third quarter calendar year 2019 (3QCY19) toxicity characteristic leaching procedure (TCLP) results

The aqueous waste from Tank 50 (salt solution) is sampled quarterly for transfers to the Saltstone Production Facility (SPF). Salt solution is treated at SPF and disposed of in the Saltstone Disposal Facility (SDF). Per request of customer, X-TAR-Z-00008, Revision 01, two SDF waste form (saltstone) samples were prepared in the Savannah River National Laboratory (SRNL) from the Tank 50 Waste Acceptance Criteria (WAC) sample and Z-Area premix material for the third quarter of calendar year 2019 (3QCY19). One sample contained a Full Premix which included 10:45:45 (by weight) of cement, slag and fly ash. The second sample contained 60:40 (by weight) of slag and fly ash only referred to as the “Cement-Free grout sample”. Results from this technical report support Task 2: ‘Grout Leaching Analyses’ of the Task Technical Request (TTR) prepared by Savannah River Remediation (SRR). After a 28 day cure, a sample of each of the SDF waste forms was collected and shipped to a certified laboratory for analysis using the Toxicity Characteristic Leaching Procedure (TCLP). The 3QCY19 saltstone (Full Premix) and the Cement-Free grout samples met the South Carolina (SC) Code of Regulations for Hazardous Waste Management Regulations (HWMR) 61-79.261.24 and 61-79-268.48 requirements for a non-hazardous waste form with respect to Resource Conservation and Recovery Act (RCRA) metals and Underlying Hazardous Constituents (UHCs), and also met the SPF WAC.

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Effect of ion interactions on the Raman spectrum of NO 3 − : Toward monitoring of low-activity nuclear waste at Hanford

Raman spectroscopy is a valuable in-situ technique for many applications. The concentrations of species in complex ionic mixtures of nuclear waste can be estimated using Raman measurements. However, it has been experimentally observed that ion interactions can cause a modification of Raman peak intensities and positions. The present work explores the nonlinear behavior associated with the nitrate anion, NO 3 − , which is present in abundance in low activity nuclear waste. We examine changes in the main Raman peak of the nitrate anion in the presence of other ions. A wide range of concentrations are covered, including those expected during direct-feed low-activity waste (DFLAW) processing at the Hanford site in the State of Washington. The experiments showed that the ions interact and associate to form ion pairs, which results in a blue shift (i.e., a shift towards higher wavenumbers) in the main Raman peak of nitrate. The results indicate that cation concentration is a better predictor of the peak shift, compared to ionic strength, both for binary and multicomponent mixtures. These findings have direct implications on the development of spectra-to-composition models for the DFLAW system, since they show deviations from the linearity assumptions used in common chemometric models.

42 ENGINEERING↗

Technology and Innovation Roadmap

This Technology and Innovation Roadmap (Roadmap) presents a comprehensive and integrated assessment of technology needs related to executing the River Protection Project (RPP) baseline, reducing risk, and providing opportunity for improvement in executing efficiencies, worker safety and environmental protection. As such, some of the proposed activities herein are pending final decision in the form of an upcoming Tri-party Holistic Agreement. Addressing the identified technology needs will contribute to achieving successful completion of the Hanford Site tank waste cleanup mission.

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Advanced Reactors Spent Fuel & Waste Science and Technology Program

Based on the higher interest in Advanced Reactor (AR) deployment (e.g., ARDP ) for potential new fuel cycles, the Spent Fuel & Waste Science and Technology (SFWST) Program has begun to evaluate the possible implications of long-term management and final disposition of potential Advance Reactor spent nuclear fuels (SNF) that would be generated in potential advanced reactors. Safely managing and dispositioning the potential future AR SNF, and any other associated radioactive wastes, is the primary focus of this initial preliminary assessment of those. This paper summarizes three primary tasks the Spent Fuel & Waste Science and Technology (SFWST) Program is executing (or collaborating on) related to the back end of the nuclear fuel cycle (BENFC) for potential future advanced reactors: 1. Advanced Reactors Spent Fuel and Waste Streams: Strategies for the BENFC This set of activities define a high-level strategy for how to systematically approach, identify, and close research and development (R&D) gaps/potential issues associated with long-term management and final disposition of AR SNF and other possible AR waste streams. This task involves summarizing advanced reactor concepts, their likely SNF and other waste forms, and identifying previous experience with similar materials, for example from DOE-managed SNF, with closely related characteristics to the potential future AR SNF. Technical R&D gaps between the breadth of detailed understanding for safe storage, transportation and disposal of the existing light water reactor SNF fuel cycle (e.g., see NASEM, 2022) and potential future fuel cycles based on advanced reactors would then be identified. 2. Characterization and Packaging Options of Advanced Reactor SNF These activities evaluate characteristics and packaging options for advanced reactor spent fuel forms. The fuel forms are categorized into three types: (1) tri-structural isotropic (TRISO), (2) metallic, and (3) fuel salt. Emphasis is given to TRISO and metallic SNF and additional waste streams from such AR as driven by the near-term anticipated operation of the Xe-100 and the Natrium reactors as advanced-reactor demonstrations1. Preliminary information for the spent-fuel salt discharged from molten-salt reactors (MSRs) is examined to provide a baseline for future efforts. All calculations and assumptions in this work are based on publicly available information. The following characteristics are calculated or estimated for use in the preliminary assessments: SNF volume and mass, radiation/activity levels through time, thermal conditions through time, potential radionuclide source terms, chemical interactions and evolutions, disposal inventories, and waste-form lifetime. Using those characteristics, calculations to determine the applicability of existing canister designs were performed. These evaluations included geometric (e.g., dimension, volume) and mass/weight considerations, known operational approaches and loading procedures, physical and chemical considerations/conditions for storage environments, as-loaded radiation, thermal, and criticality analyses to identify constraints for storage, transportation, and disposal. 3. Back-End Management of Advanced Reactors (BEMAR) The DOE NE-8 organization has defined an Integrated Project Team to evaluate the Back End Management of Advanced Reactors (BEMAR) (includes DOE staff from a range of organizations (e.g., NE-81, NE-82, OCED) and national laboratory technical staff within the DOE NE-81 and NE-82 programs). This BEMAR group works directly with advance reactors developers to assess for the DOE the technical feasibility of storage, transportation, and disposal of AR SNF based on the characteristics provided by the developers to DOE (much of which is proprietary). The BEMAR is also tasked to develop rough-order-of-magnitude cost estimates to compare the waste management system for individual advanced reactors to existing light-water reactor management practices. To accomplish this, the BEMAR group is implementing a Systems Engineering approach.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Analcime-wairakite formation during experimental cement-bentonite alteration at 200–300 °C

Engineered barrier system materials in nuclear waste repositories may undergo hydrothermal alteration in response to groundwater saturation and heating events over their long operational timescales. Hydrothermal interactions between engineered materials (e.g., bentonite buffers, cements, waste canister materials) and the host rock environment may drive alteration processes that affect the advantageous properties of some barrier materials. However, such alteration will also promote the formation of zeolites, hydrothermally formed minerals that may themselves act to isolate radionuclides. Understanding the environmental conditions that control radionuclide-sorbing properties of zeolites, such as Si/Al ratio or Na content, will be valuable for assessing the changing properties of engineered barrier materials in the case of an in situ heating event. Here, we present experimental work characterizing the formation of zeolites during hydrothermal interactions between generic clay and cement barrier materials, with a focus on the analcime-wairakite zeolite series, which has known radionuclide sorption and exchange properties. We present the results of hydrothermal experiments combining uncured ordinary Portland cement powder with steel and Wyoming bentonite in the presence of Opalinus clay and a synthesized Opalinus clay groundwater to simulate water-saturated conditions in an argillaceous rock repository. The experiments were conducted isothermally at 200 or 300 °C for 8 to 24 weeks. In contrast to analogous studies that did not include cement reactants, we observed the formation of analcime-group minerals in all experiments. The addition of cement resulted in lower Si/Al ratios in the zeolites compared to similar studies that did not include cement. The presence of cement as a reactant was interpreted to promote analcime formation at 200 °C. At 300 °C, we observed higher calcium and silica concentrations in the aqueous solutions as well as increased wairakite formation and decreased analcime formation compared to the experiments at 200 °C. These results show a fully realized analcime-wairakite solid solution that falls between Si/Al = 2 (ideal) and a trend of analcime minerals that have increasing Si/Al ratios with increasing Na/(Na+Ca). Our results show predictable relationships between the Si/Al ratio and the analcime-wairakite content under hydrothermal conditions and illustrate that repository material interactions may promote the formation of zeolites in the analcime-wairakite solid-solution series during heating events in the subsurface.

58 GEOSCIENCES↗