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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Electrically regenerated ion-exchange technology: Leveraging faradaic reactions and assessing the effect of co-ion sorption

Capacitive deionization (CDI) technologies have the potential to become cost-competitive alternatives to reverse osmosis for the treatment of brackish waters. In this study, we describe our findings on the effect of co-ion sorption and faradaic side reactions on our ion exchange resin functionalized desalination electrodes which passively capture salt and reject it upon charging. This system, which we previously reported on and refer to as electrically regenerated ion exchange (ERI), avoids the use of expensive ion exchange membranes in an effort to save costs. Surprisingly, we find that, compared to a reference CDI system, ERI electrodes capture salt most effectively at low applied voltages (0.5 mg/cm 3 at 0.8 V). Both CDI and ERI systems also seem to suffer from co-ion sorption effects which negatively impact salt adsorption. However, Faradaic side reactions at higher voltages (1 V and 1.2 V) which we track via pH measurements, serve as a detriment to CDI but seem to facilitate the functionality of ERI.

42 ENGINEERING↗
DOE OSTI2022

Insights into Sorption and Molecular Transport of Aqueous Glucose into Zeolite Nanopores

Liquid-phase heterogeneous catalysis using zeolites is important for biomass conversion to fuels and chemicals. There is a substantial body of work on gas-phase sorption in zeolites with different topologies; however, studies investigating the diffusion of complex molecules in liquid medium into zeolitic nanopores are scarce. Here, we present a molecular dynamics study to understand the sorption and diffusion of aqueous β-d-glucose into β-zeolite silicate at T = 395 K and P = 1 bar. Through 2-μs-long molecular dynamics trajectories, we reveal the role of the solvent, the kinetics of the pore filling, and the effect of the water model on these properties. We find that the glucose and water loading is a function of the initial glucose concentration. Although the glucose concentration increases monotonically with the initial glucose concentration, the water loading exhibits a nonmonotonic behavior. At the highest initial concentration (~20 wt %), we find that the equilibrium loading of glucose is approximately five molecules per unit cell and displays a weak dependence on the water model. Glucose molecules follow a single-file diffusion in the nanopores due to confinement. Here, the dynamics of glucose and water molecules slows significantly at the interface. The average residence time for glucose molecules is an order of magnitude larger than that in the bulk solution, while it is about twice as large for the water molecules. Our simulations reveal critical molecular details of the glucose molecule’s local environment inside the zeolite pore relevant to catalytic conversion of biomass to valuable chemicals.

09 BIOMASS FUELS↗
DOE OSTI2022

Isotherm Model for Moisture-Controlled CO 2 Sorption

Moisture-controlled sorption of CO 2 , the basis for moisture-swing CO 2 capture from air, is a novel phenomenon observed in strong-base anion exchange materials. Prior research has shown that Langmuir isotherms provide an approximate fit to moisture-controlled CO 2 sorption isotherm data. However, this fit still lacks a governing equation derived from an analytic model. As such, in this paper we derive an analytic form for an isotherm equation from a bottom-up approach, starting with a fundamental theory for an alkali liquid. In the range of interest relevant to CO 2 capture from air, an isotherm equation for an alkali liquid reduces to a simple analytic form with a single parameter, $K_{\text{eq}}$. In the limit $K_{\text{eq}} \gg 1$, a 2nd order approximation simplifies to a Langmuir isotherm that, however, deviates from experimental data. The isotherm theory for an alkali liquid has been generalized to a strong-base anion exchange material. In a strong-base anion exchange material, water concentration inside a sorbent, [H 2 O], is not large enough to be regarded as constant, which allows us to extend $K_{\text{eq}}$ to $K_{\text{eq(AEM)eff}} = K_{\text{eq(AEM)}} \times$ [H 2 O]$^{–n}$ according to the law of mass action. The final isotherm formula has been validated by experimental data from the literature. For a moisture-controlled CO 2 sorbent, $K_{\text{eq(AEM)eff}}$ varies significantly with moisture content of the sorbent. Depending on moisture level, the observed $K_{\text{eq(AEM)eff}}$ in a specific sorbent ranges from a few times to a few thousand times the value of $K_{\text{eq}}$ of a 2 mol L –1 alkali liquid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Kinetic Model for Moisture-Controlled CO 2 Sorption

The understanding of the sorption/desorption kinetics is essential for practical applications of moisture-controlled CO 2 sorption. We introduce an analytic model of the kinetics of moisture-controlled CO 2 sorption and its interpretation in two limiting cases. In one case, chemical reaction kinetics on pore surfaces dominates, in the other case, diffusive transport through the sorbent defines the kinetics. Here, we show that reaction kinetics, which is dominant in the first case, can be expressed as a linear combination of 1st and 2nd order kinetics in agreement with the static isotherm equation derived and validated in a previous paper. The interior transport kinetics can be described by non-linear diffusion equations. By combining all carbon species into a single equation, we can eliminate — in certain limits — the source terms associated with chemical reactions. In this case, the governing equation is ∂θ/∂t = –∇ · (–D eff ∇ θ ). For a sorbent in a form of a flat sheet or a membrane, one can maintain the same functional form of a diffusion equation by introducing a generalized effective diffusivity D M that combines contributions from both surface chemical reaction kinetics and interior diffusive transport kinetics. Experimental data of transient CO 2 flux in a preconditioned commercial anion exchange membrane fit well to the 1st order model as long as very dry states are avoided, validating the theory. The observed DM for a preconditioned commercial anion exchange membrane ranges from 6.6× 10 -14 to 7.1× 10 -14 m 2 s -1 at 35°C. These small values compared to typical ionic diffusivities imply a very slow kinetics, which will be the largest issue that needs to be addressed for practical application. The collected transient CO 2 flux data are used to predict the magnitude of a continuous CO 2 pumping flux in an active membrane that transports CO 2 against a CO 2 concentration gradient. The pumped CO 2 flux is supported by water flux due to a water concentration gradient.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Sorption Enhanced Mixed Matrix Membranes for Hydrogen (H 2 ) Purification and Carbon Dioxide (CO 2 ) Capture

The technical objective of this project was to develop sorption enhanced mixed matrix membranes with H 2 permeance of 500 gas permeance units (GPU) and H 2 /CO 2 selectivity of 30 at 150-200 °C. These membranes will be the central component in the design of membrane based systems for 90% capture of CO 2 from coal-derived syngas, with 95% CO 2 purity at a cost of electricity 30% less than baseline capture approaches. The unique approach in this proposal is to design crosslinked polymers containing Pd-based nanoparticles achieving strong H 2 sorption and size sieving ability and thus H 2 /CO 2 selectivity. The specific objectives for each budget period (BP) are described below. BP 1: Identify polymer matrix with strong size sieving ability and palladium (Pd)-containing nanomaterials to prepare freestanding mixed matrix films with H 2 permeability of 50 Barrer and H 2 /CO 2 selectivity of 30 at 150-200°C with simulated syngas. BP 2: Prepare and optimize thin film mixed matrix composite membranes materials with H 2 permeance of 500 GPU and H 2 /CO 2 selectivity of 30 at 150-200 °C, and complete the modification of the membrane test unit for the field test in the BP 3. BP 3: Conduct a 20-day field test of the membranes with real syngas at Center for Advanced Energy Research (CAER) of the University of Kentucky (UKy). During the BP2, we have successfully prepared thin-film composite (TFC) membranes based on mixed matrix materials (MMMs) containing Pd nanoparticles in polymers, and demonstrated their superior and robust performance for H 2 /CO 2 separation at 150 – 225 °C. (1) Production of the Pd based nanoparticles with a diameter of 4 nm has been scaled up to 200 mg/day. (2) We have prepared TFC membranes with H 2 permeance above 500 GPU and H 2 /CO 2 selectivity above 30 at temperatures up to 225 °C, which meet the targets for the BP2. (3) We have conducted parametric studies of TFC membranes with a mixed gas containing H 2 S and H 2 O and demonstrated the stability of the membranes. (4) We have established a new testing plan at the Center for Advanced Energy Studies (CAER) at the University of Kentucky because NCCC decided to shut down their gasifier. During this project, four Ph.D. students received the inter-disciplinary training and graduated, including Shailesh Konda, Maryam Omidvar, Deqiang Yin, and Lingxiang Zhu. One postdoctoral researcher (Dr. Liang Huang) and two Ph.D. students (Abhishek Kumar and Hien Nguyen) are involved in this project. The project leads to one provisional patent application, eight peer-reviewed articles, and one manuscript in preparation. The details are shown below.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2020

Mobile Sorption-based Thermal Battery for Harvesting Low-Temperature Geothermal Energy

Around 20% of the total primary energy in the United States is consumed for thermal demands of buildings such as space cooling, dehumidification, and space heating (EIA 2018). Low-temperature geothermal energy is abundant and can effectively satisfy buildings’ thermal demands. However, low-temperature geothermal energy is underutilized because the energy density of geothermal fluid is too low to justify the costs associated with transporting it between existing geothermal resources and buildings. The mobile sorption-based thermal battery (MSTB) system has been developed using three-phase (i.e., vapor–liquid, solution–solid, crystal) sorption technology to harvest low-temperature heat and store it with a much higher energy density than the geothermal fluid. The energy density of salt crystals is over six times higher than geothermal fluid, which makes long-distance transportation of salt crystals economically feasible. Salt crystals can be used to dehumidify air or provide space cooling in buildings, which alleviates peak demand on the electricity grid by offsetting electricity use for these end uses. This helps improve the grid’s stability and resilience. High-energy storage density, fast crystallization, and dissolution of salt crystals are all critical to the viability and performance of the MSTB system. Therefore, the design and operation of MSTB systems need to ensure effective generation and dissolution of salt crystals inside the MSTB. To achieve this target, this seedling project developed an experimental apparatus for characterizing the crystallization and dissolution processes. The energy density and potential latent cooling capacity of the MSTB are also evaluated based on lab test results. The crystallization results showed that the generated lithium chloride hydrate crystals are fluffy, the crystallization process lasts about 50 min, and the maximum crystal fraction (i.e., the ratio of crystal mass to the mass in the MSTB) can be up to 51.1% of the total mass in the MSTB at a solution flow rate of 1.58 g/s. The dissolution results show that the salt crystals in the MSTB can be fully dissolved within 15–28 min, based on different test conditions. Reducing solution flow rate and cooling water temperature can achieve increased energy storage density and crystal fraction. While the increase in the discharge rate (i.e., latent cooling capacity for dehumidifying air) is achieved by increasing flow rate and temperature of inlet diluted solution, as well as by using a pump for internal solution circulation, the discharge rate increases by 38%, from 0.95 kW to 1.31 kW. Compared with increasing the inlet solution flow rate, power consumption of salt solution transportation can be reduced by using a pump for internal solution circulation. The crystallization test results also showed that the maximum energy storage density is 981.8 kJ/kg, and the maximum discharge rate of the dissolution tests is ≤1.79 kW. Both are above the target values of 900 kJ/kg and 1.75 kW) for this project. The work reported here proves the feasibility and advancement of the MSTB system, which is helpful to the further study and improvement of the MSTB system.

15 GEOTHERMAL ENERGY↗
DOE OSTI2023

Moisture Sorption and Swelling of Sylgard-184

The report summarizes the quantitative assessment of moisture sorption by Sylgard-184. It is an important ingredient in many of our materials. Moisture sorption for this material has been extensively studied with data from 9 different samples available for analysis. These samples varied in size and geometry. Seven of the 9 samples were thin slabs. The remaining 2 were cylinders, one of which had comparable height and diameter and is therefore considered a 3-D sample. All the samples, except 2 (1D_slab4.06mm and 1D_Sylgard_2016_Sharma) belonged to lot number A1606324. They were all prepared by Tony Rodrigues in the plastics shop in the Summer of 2016 and tested by Hom Sharma between October 2016 and June 2017. 1D_slab4.06mm was also prepared by Tony Rodrigues in the plastics shop in Summer of 2016, however, the sample did not have a lot number. 1D_Sylgard_2016_Sharma was prepared by Hom Sharma in February 2016 and tested potentially around May - June 2016.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

M3SF-24LL010301062-Surface Complexation/Ion Exchange Data Integration for Radionuclide Sorption to Clay Minerals

This progress report (Level 3 Milestone Number M3SF-24LL010301062) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Argillite International Collaborations Work Package SF-24LL01030106. The activity is focused on our long-term commitment to engaging our partners in international nuclear waste repository research. The focus of this milestone is the establishment of international collaborations for sorption modeling and the associated impacts of unlocking larger, community-based datasets. More specifically, we are developing a database framework for Spent Fuel and Waste and Science Technology (SFWST) that is aligned with the Helmholtz Zentrum Dresden Rossendorf (HZDR) and other international sorption database development groups in support of the database needs of the SFWST program.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

A computational pipeline to generate a synthetic dataset of metal ion sorption to oxides for AI/ML exploration

The charged mineral/electrolyte interfaces are ubiquitous in the surface and subsurface–including the surroundings of the geological disposal sites for radioactive waste. Therefore, understanding how ions interact with charged surfaces is critically important for predicting radionuclide mobility in the case of waste leakage. At present, the Surface Complexation Models (SCMs) are the most successful thermodynamic frameworks to describe ion retention by mineral surfaces. SCMs are interfacial speciation models that account for the effect of the electric field generated by charged surfaces on sorption equilibria. These models have been successfully used to analyze and interpret a broad range of experimental observations including potentiometric and electrokinetic titrations or spectroscopy. Unfortunately, many of the current procedures to solve and fit SCM to experimental data are not optimal, which leads to a non-transferable or non-unique description of interfacial electrostatics and consequently of the strength and extent of ion retention by mineral surfaces. Recent developments in Artificial Intelligence (AI) offer a new avenue to replace SCM solvers and fitting algorithms with trained AI surrogates. Unfortunately, there is a lack of a standardized dataset covering a wide range of SCM parameter values available for AI exploration and training–a gap filled by this study. Here, we described the computational pipeline to generate synthetic SCM data and discussed approaches to transform this dataset into AI-learnable input. First, we used this pipeline to generate a synthetic dataset of electrostatic properties for a broad range of the prototypical oxide/electrolyte interfaces. The next step is to extend this dataset to include complex radionuclide sorption and complexation, and finally, to provide trained AI architectures able to infer SCMs parameter values rapidly from experimental data. Here, we illustrated the AI-surrogate development using the ensemble learning algorithms, such as Random Forest and Gradient Boosting. These surrogate models allow a rapid prediction of the SCM model parameters, do not rely on an initial guess, and guarantee convergence in all cases.

Li, Chunhui↗
DOE OSTI2020

A Novel High Energy Density Sorption-based Thermal Battery for Low-grade Thermal Energy Storage

Thermal energy storage (TES) can alleviate peak demand on the electricity grid by offsetting building thermal loads, increasing the grid’s reliability and resilience. However, low energy density and poor energy performance of existing TES technologies limit their applications. Sorption-based thermal battery (STB) system is thus developed using three-phase sorption technology to harvest low-temperature heat, store it with a much higher energy density than common TES systems and dehumidify air or provide space cooling in buildings. Although STB has been experimentally proved to be feasible, influencing factors on its performance are still unknown by far. Therefore, this paper conducted a parametric analysis on crystallization and crystal dissolution performance of a developed STB test rig. The crystallization results showed that the energy density of the STB increased with reducing the solution flow rate and the cooling water temperature. The dissolution results showed that a higher discharge rate of the STB can be achieved with increasing the flow rate and temperature of inlet diluted solution. The work in this study is helpful to the optimal design and operation of the STB system.

Wang, Lingshi↗
DOE OSTI2023

CO2 Sorption in Aminopolymer-Based Direct Air Capture Composites Through Fluorescent Detection

Aminopolymer-mesoporous oxide composites are becoming widely recognized for their ability to adsorb CO2 directly from the air. However, a better fundamental understanding of the nature of these materials under different environmental operating conditions will be necessary before they become ubiquitous in industrial direct air capture (DAC) systems. For example, gas diffusion in general is coupled with polymer segmental mobility in these composites; diffusion is therefore affected by interactions of the polymer with the pore wall of the mesoporous oxide, by the relative humidity of the air, and by electrostatic crosslinks that develop as a function of CO2 sorption. Disentangling these and additional complicated effects in order to better optimize operating conditions is a major challenge for the field. Here, we present a method for quantifying the adsorption of CO2 and moisture in a polyethylenimine (PEI) - Al2O3 composite using infrared sensing while we simultaneously monitor polymer mobility with a fluorescent probe molecule doped into the composite. Both the fluorescence intensity and shape of the emission spectra are strongly dependent on the mobility of the supporting medium. We monitor the polymer mobility and CO2 adsorption kinetics across a series of different relative humidities (RH) with this technique, and we observed that the relative difference between polymer mobility and sorption kinetics from one RH to the next are quite dramatic. We interpret these results and discuss how they can be used to inform the design of more efficient DAC systems for real-world operating conditions.

carbon capture↗
DOE OSTI2021

Evaluation of engineered sorbents for the sorption of mercury from contaminated bank soils: a column study

Abstract As a global environmental pollutant, mercury (Hg) threatens our water resources and presents a substantial risk to human health. The rate and extent of immobilization of Hg 2+ (hereafter, Hg) on engineered sorbents (Thiol-SAMMS®, pine biochar, SediMite™, Organoclay™ PM-199, and quartz sand as a control) was evaluated using flow-through column experiments. The effectiveness of the sorbents was based on (1) the percentage of Hg removed in relation to the total amount of Hg passing the sorbent column, and (2) the rate of Hg uptake compared to the nonreactive tracer bromide (Br − ). All sorbents removed Hg to a certain extent, but none of the sorbents removed all the Hg introduced to the columns. Thiol-SAMMS showed the highest mean percentage of Hg removed (87% ± 2.9%), followed by Organoclay PM-199 (71% ± 0.4%), pine biochar (57% ± 22.3%), SediMite (61% ± 0.8%), and the control quartz sand (11% ± 5.6%). Thiol-SAMMS was the only sorbent to exhibit retardation of Hg in comparison to the conservative tracer Br − . For the remaining sorbents, Br − along with low concentrations of Hg were eluted within the first 3 pore volumes, indicating limited retardation of Hg. Overall, removal of Hg by sorbents was substantial, suggesting that sorbents might be suitable for deployment in contaminated environments. High concentrations of DOM leaching from the soil columns likely influenced the speciation of Hg and inhibited sorption to the sorbents. Incomplete removal of Hg by any sorbent suggests that additional optimization is needed to increase efficiency.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Investigation of competitive sorption and plasticization of hyperaged CANAL ladder polymers for acid gas purification

Identifying membrane materials that have exceptional separation performance and stability to complex CO 2 -containing mixtures is a pressing topic in separation science. In this work, the membrane separation performance for a recently discovered class of contorted polymers synthesized via catalytic arene-norbornene annulation (CANAL) polymerization is presented. These CANAL polymers achieve high CO 2 /CH 4 selectivity of 68 after physical aging (up to ∼1 year), which significantly augments the size-sieving capabilities of the membranes. Binary CO 2 /CH 4 and ternary H 2 S/CO 2 /CH 4 testing result in a 41 % and 50 % enhancement in selectivities, respectively, for hyperaged (∼1 year) contorted CANAL polymers, highlighting their size-sieving capabilities. The remarkably high CO 2 /CH 4 mixed-gas and combined acid gas (CAG, (CO 2 +H 2 S)/CH 4 ) selectivities of 88 and 95, respectively, for CANAL-Me-S 5 F in particular surpass both the 2018 CO 2 /CH 4 mixed-gas and CAG upper bounds. Performance stability was also investigated for high concentrations of CO 2 , revealing a reduction in CO 2 /CH 4 mixed-gas selectivity without compromising CO 2 permeability, suggesting strong sorption of CO 2 but minimal plasticization effects for short testing periods. In addition, time-dependent plasticization shows negligible effects on CO 2 /CH 4 mixed-gas selectivity despite an increase in CO 2 permeability when exposed to high concentrations of plasticizing CO 2 over an extended period of 170 h. This study provides valuable insights into hyperaged CANAL polymers and their performance in practical industrial processes.

03 NATURAL GAS↗
DOE OSTI2025

Liquid Sorption-Enhanced Haber–Bosch Process

The use of a liquid sorbent in a traditional Haber-Bosch process enables significant improvements in energy efficiency and potential cost savings for arguably the most important chemical process on the planet. The approach presented in this report employs an incompressible liquid sorbent that absorbs and releases ammonia (NH 3 ) under specific conditions. To achieve this, we investigate reactions of ammonia and pure phosphoric acid (H 3 PO 4 , PA), which rapidly neutralize to form an equilibrated solution of monoammonium phosphate (MAP) and diammonium phosphate (DAP) that functions as a reversible and regenerable sorbent. Through intimate contact of the gas-phase Haber-Bosch reaction mixture with this liquid absorbent, complete equilibrium uptake may be achieved in an appropriately sized separator, and facile separation occurs through the use of independent liquid and gas phases. Following depressurization and release of the ammonia product, only the incompressible fluid needs to be repressurized and returned to the reactor. This study documents proof-of-concept absorption and desorption experiments carried out in 75 mL batch reactors, predominantly charged with precise MAP and DAP mixtures that equilibrate at process-relevant temperatures and pressures. We then assemble the first thermodynamic relationships that underlie this advantaged separation strategy, validated by reactive force field (ReaxFF) interatomic potential simulations, and benchmarked with traditional separation routes via process modeling and technoeconomic analysis. The scale of energy consumption in the century-old Haber-Bosch process is massive, and the elegant liquid sorption approach reported here offers opportunities to enhance its energy efficiency for the next frontier of ammonia synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Final Report: Process Intensification of Hydrogen Production through Sorption-Enhanced Gasification of Biomass

The University of Utah, in partnership with Idaho National Laboratory (INL), evaluated Sorption-Enhanced Gasification (SEG) as a transformative pathway for producing hydrogen with the potential for negative CO 2 emissions. SEG integrates gasification, water-gas shift, and in-situ carbon capture within a dual fluidized bed reactor to enable efficient clean hydrogen production. Key challenges related to biomass variability and process complexity were addressed through feedstock engineering, reaction optimization, and process validation. A co-pelletized biomass–limestone feedstock was developed to simplify feeding and introduction of makeup limestone. Kinetic and sorbent studies identified optimal operating conditions and confirmed the suitability of low-cost limestone, while catalysts were developed to reduce tar formation. Reactor modeling and techno-economic analysis indicated that SEG can achieve competitive hydrogen production costs, particularly when combined with carbon incentives, supporting its potential for scale-up and carbon-negative operation.

08 HYDROGEN↗
DOE OSTI2020

Estimation of Sorption Behavior of Europium to Calcium Silicate Hydrate by Thermal Analysis - 20172

High-level radioactive waste generated from reprocessing processes will be disposed in a geological disposal that is deep underground. Calcium silicate hydrate is formed as a secondary mineral in the repository via the reaction of calcium ions leaching from the cement and the silicic acid dissolved from the host rocks. In this study, the sorption behavior of europium, which is also known as a chemical analog of americium, on calcium silicate hydrate was examined. The solid phase was analyzed via thermogravimetry- differential thermal analysis, differential scanning calorimetry, Raman spectroscopy, fluorescence spectroscopy, and fluorescence lifetime analysis. To understand the behavior of calcium silicate hydrate under conditions saturated with groundwater, the study samples were analyzed using the above methods, except for deferential scanning calorimetry, without a drying process. The results of the differential scanning calorimetry analyses showed that the temperatures for the endothermic peaks of calcium silicate hydrate for the lower Ca/Si ratios were larger than those for the higher Ca/Si ratios for coexistent conditions of europium ions. Hence, the relationships of the temperatures of the endothermic peaks and the Ca/Si ratios were reversed by the addition of europium ions. These study results suggest that calcium silicate hydrate can immobilize europium ions, thus preventing the production of colloidal forms. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

The Impact of Ethylenediaminetetraacetic Acid (EDTA) on the Sorption of Nd(III), Th{sup (IV)}, and U(VI) onto Dolomite in WIPP-Relevant Brines, GWB and ERDA-6 - 20356

Storage of legacy, transuranic waste at the Waste Isolation Pilot Plant (WIPP) requires accurate risk models for performance assessments. These models must predict the long-term fate and transport of contaminants in the WIPP and surrounding environment. Laboratory support is necessary for the development of an accurate model through better understanding of contaminant behavior in the WIPP. The WIPP is a deep geologic repository that is characterized by high ionic strength due to evaporite deposits in the Salado formation (porewaters up to 7.4 M). High concentrations of sodium chloride (NaCl), calcium chloride (CaCl{sub 2}), and magnesium chloride (MgCl{sub 2}) are particularly of concern due to their potential impact on solubility and ultimately transport of contaminants of concern. Additionally, ligands capable of forming strong complexes with metals are found in significant concentrations in the WIPP environment due to their disposal from waste processing and formation during degradation of repository components (e.g. cellulose degradation by calcium hydroxide in cement). Consequently, there is a need to investigate the fate and transport of contaminants in the WIPP environment with a focus on the effects of high ionic strength and strongly coordinating ligands. Contaminants of high concern include the actinides (U(VI), Pu(IV), and Am(III)). Laboratory support of the WIPP modeling efforts was provided by this research. A series of batch experiments were utilized to study the impact of ionic strength, contaminant concentration, and the presence of ethylenediaminetetraacetic acid (EDTA) on the sorption of Nd(III), Th(IV), and U(VI) onto dolomite, a carbonate mineral found within the Culebra formation. The Culebra formation is the most transmissive layer above the WIPP, making transport of contaminants the most likely route in previous risk assessments. Two brines specifically designed to imitate conditions within the WIPP environment were used in these experiments. The U.S. Energy Research and Development Administration Well 6 (ERDA-6, 95%) brine simulates a low Mg environment, while the generic weep brine (GWB, 95%) simulates the WIPP environment with a high Mg concentration. Mg is added to the repository in the form of MgO as an engineered barrier and is naturally present in some formations. It is expected to scavenge carbonate from solutions decreasing formation of the highly soluble and competitive uranium-carbonate complexes. EDTA is used during manipulations of nuclear materials due to its ability to form strong, stable complexes with the actinides and may be found in high concentrations (up to 0.08 mM) within the WIPP as waste canisters degrade. Further, it may provide additional avenues for unwanted transport of contaminants. Nd(III) and Th(IV) were used as stable analogues of Am(III) and Pu(IV), respectively, to represent the most common oxidation states of actinides in the WIPP environment in addition to U(VI). The potential for colloid formation was also investigated with low and high concentrations of contaminants (10 and 1000 μg/L) using three size-dependent particle separation steps. The results of this research provide a better understanding of potential behavior of actinides in the presence of EDTA and within WIPP-relevant brines. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗