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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Ion correlations drive charge overscreening and heterogeneous nucleation at solid–aqueous electrolyte interfaces

Significance Ion distributions at charged solid–water interfaces, referred to as the electrical double layer (EDL), are poorly understood at high ion concentrations, in part due to the lack of molecular-scale descriptions of the interactions between adsorbed hydrated ions. Here, direct visualization of the salinity-dependent evolution of EDL structure reveals molecular origins of nonclassical transformation of the EDL, in which charge overscreening and heterogeneous nucleation are driven by ion–ion correlations at the interfaces. This manifestation of the atomistic basis of nonclassical behaviors provides a much-needed understanding of the impact of ion cooperativity at charged interfaces for the development of predictive models for element transport in natural environments and advanced technologies for material growth and synthesis in saline environments.

36 MATERIALS SCIENCE↗
DOE OSTI2020

DOE Award No.: DE-FE0023919 Phase 3 Scientific/Technical Report

This is the Phase 3 Report for the ‘Deepwater Methane Hydrate Characterization and Scientific Assessment or Genesis of Methane Hydrates in the Gulf of Mexico (GOM2)’ research project (DOE Award No. DE-FE0023919). The report summarizes activities from January 16, 2018 to September 30, 2019. The project is led by the University of Texas at Austin (UT). The objective is to gain insight into the nature, formation, occurrence and physical properties of methane hydrate-bearing sediments for the purpose of methane hydrate resource appraisal through the planning and execution of drilling, coring, logging, testing and analytical activities that assess the geologic occurrence, regional context, and characteristics of marine methane hydrate deposits in the Gulf of Mexico outer continental shelf (OCS). We determined that it would not be possible to pursue the project with the International Ocean Discovery Program (IODP) and then developed a revised science and operations plan to maximize the science using a commercial vessel within the budget that is available. We improved the scientific capability of the UT pressure core center by adding the ability to X-ray pressure cores, and the ability to cut and store multiple core samples for experimental analysis. We transferred pressure cores to peer institutions, including the National Energy Technology Lab (NETL) the United States Geological Survey (USGS Woods Hole). We made advances in understanding the composition and source of gasses locked in the methane hydrate from Green Canyon 955 (GC-955). We developed approaches to determine the in-situ salinity of hydrate-bearing samples, revealing that the in situ salinity of the GC 955 reservoir is just above that of seawater. We determined that the GC-955 hydrate reservoir is composed of sandy silt with a high concentration of hydrate interbedded with clayey silt with no hydrate present. We determined that some or all of the intervals bounding the hydrate reservoir are composed of material similar to the reservoir (sandy silt with hydrate and clayey silt with no hydrate), but with a lower net to gross. We determined that the reservoir effective permeability at a hydrate saturation of ~80-90 % is ~0.1 mD (or 1.0×10-16 m2) to ~0.5 mD (or 5.0×10-16 m2) and the intrinsic permeability is ~12 mD (or 1.2×10-14 m2). The GC-955 reservoir in-situ porosity of sandy silt is 0.38 to 0.40 and is largely independent of effective stress, and that the porosity of clayey silt is 0.33 at an in situ effective stress of 3.8 MPa to ~0.37 at zero effective stress. We developed a systematic, repeatable approach to studying hydrate reservoir properties by reconstituting individual lithofacies from dissociated pressure cores. We determined index properties of GC-955 reservoir, including liquid limit and plasticity, porosity, capillary behavior, and particle size distribution. We developed a more robust pressure coring technology. We finalized and published the UT-GOM2-1 Expedition Volume and we finalized a dedicated volume on the UT-GOM2-1 expedition that will be published in the American Association of Petroleum Geologists Bulletin (AAPG) in spring 2020.

03 NATURAL GAS↗
DOE OSTI2022

Modern analogs for understanding pollen-vegetation dynamics in a Mediterranean mosaic landscape (Balearic Islands, Western Mediterranean)

This paper presents the study of modern pollen analogs from the Balearic Islands. While similar studies have been largely applied to mainland areas, research focused on modern vegetation dynamics on Mediterranean islands remains very rare. In this research, we combine vegetation surveys, pollen analysis and multivariate statistics to understand landscape composition. The main objectives of are: (1) to examine pollen-vegetation relationships in relation to environmental and land-use variables; (2) to understand modern pollen representation in a mosaic landscape structure; and (3) to propose pollen indicators that characterize the primary vegetation types from the Balearic Islands to better interpret past pollen records in Mediterranean island environments. Pollen results and Redundancy Analysis (RDA) distinguish three major groups: (a) Holm oak and box formations; (b) maquis and garrigues; and (c) anthropogenic and open habitats. Landscape form, mean decadal rainfall, mean decadal temperature, fire activity, trampling, slope percentage, wet/flooded soil, saline soil, distance to agropastoral cells, gHM index, domestic herbivory presence, agropastoral use, and soil type are the major variables explaining modern pollen assemblage variation in our research. Poaceae undiff., Plantago sp., Apiaceae undiff., Cerealia-t, and Cichorieae are highly correlated to human activities but should be interpreted cautiously when occurring in low values. Quercus ilex-t, Hypericum, and Buxus are correlated to humid locations while Pistacia, Pinus, Juniperus-t, and Olea to high mean decadal temperatures. Our study indicates how pollen analysis and multivariate analysis are powerful tools for characterizing the mosaic landscape, with special focus on the main vegetation types of the Balearic Islands.

Geology↗
DOE OSTI2020

DISCOVR: Development of Integrated Screening, Cultivar Optimization, and Verification Research

The DISCOVR consortium has developed and is applying an integrated platform and workflow for standardized, deep characterization of highly productive and resilient microalgae strains. New strains are screened using three consecutive tiers in a conceptual down-selection funnel to arrive at the most promising strains. At tier I, strains are screened on gradient incubators to determine their temperature and salinity tolerance range, and to evaluate their resistance to infectious agents (e.g., chytrids). At tier II, the strains’ winter and summer season biomass productivities are quantified in Laboratory Environmental Algae Pond Simulator (LEAPS) photobioreactors, and biomass composition is determined under N-replete and N-deplete conditions. At tier III, the best winter and summer season strains are evaluated in indoor crash ponds to determine their resilience to induced infections, and strains are tested in outdoor raceway ponds to confirm high biomass productivity and culture stability. The top strains are then evaluated in seasonal SOT outdoor pond culture trials at AzCATI, the dedicated Department of Energy SOT (State of Technology) testbed. Additional research is carried out on evaluating growth promoting molecules, reducing the impact of oxygen inhibition, optimizing pond operational conditions, measuring compositional shift dynamics, developing integrated pest management strategies, analysing culture health using 96 well-plate tools, implementing spectroradiometric monitoring and using machine learning to predict culture crashes.

Huesemann, Michael H↗
DOE OSTI2020

A Satellite-Derived Upper-Ocean Stratification Data Set for the Tropical North Atlantic With Potential Applications for Hurricane Intensity Prediction

Upper-ocean stratification strongly impacts vertical mixing and the heat flux between the ocean and atmosphere, especially under extreme conditions of tropical cyclones (TCs). Knowledge of prestorm stratification is important for accurate TC intensity prediction. In situ observations of the tropical ocean have significantly increased in the past decade. However, they are still too sparse to resolve ocean stratification variability in near-real time and on small spatial scales. Here, in this study, based on long-term observations and an ocean reanalysis data set from 2004–2017, we investigate the possibility of retrieving upper-ocean stratification from sea surface temperature (SST), sea surface salinity (SSS), and sea surface height (SSH) using a simple regression method. It is found that more than 90% of the mean seasonal cycle and about 30% to 80% of temperature and salinity stratification anomalies can be reconstructed using surface data from either observations or an ocean reanalysis. Simple regression can be used with satellite observations to create a high-resolution, near-real-time-gridded ocean stratification data set that successfully reproduces both the large and mesoscale variability of ocean stratification. When used in a simple expression for TC-induced SST cooling, the satellite-derived stratification shows improvements over an ocean analysis in terms of variance explained of SST cooling, offering promise as a near-real-time indicator of the ocean's impact on TC intensification.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Picochlorum celeri as a model system for robust outdoor algal growth in seawater

Abstract With fast growth rates, broad halotolerance and the ability to thrive at high temperatures, algae in the genus Picochlorum are emerging as promising biomass producers. Recently, we isolated a remarkably productive strain, Picochlorum celeri , that attains > 40 g m −2 day −1 productivities using simulated outdoor light. To test outdoor productivities, Picochlorum celeri was cultivated in 820 L raceway ponds at the Arizona Center for Algae Technology and Innovation. Picochlorum celeri demonstrated the highest outdoor biomass productivities reported to date at this testbed averaging ~ 31 g m −2 day −1 over four months with a monthly (August) high of ~ 36 g m −2 day −1 . Several single day productivities were > 40 g m −2 day −1 . Importantly for sustainability, Picochlorum celeri achieved these productivities in saline water ranging from seawater to 50 parts per thousand sea salts, without any biocides or pond crashes, for over 143 days. Lastly, we report robust genetic engineering tools for future strain improvements.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Uncultivated Viral Populations Dominate Estuarine Viromes on the Spatiotemporal Scale

Viruses are ubiquitous and abundant in the oceans, and viral metagenomes (viromes) have been investigated extensively via several large-scale ocean sequencing projects. However, there have not been any systematic viromic studies in estuaries. Here, we investigated the viromes of the Delaware Bay and Chesapeake Bay, two Mid-Atlantic estuaries. Deep sequencing generated a total of 48,190 assembled viral sequences (>5 kb) and 26,487 viral populations (9,204 virus clusters and 17,845 singletons), including 319 circular viral contigs between 7.5 kb and 161.8 kb. Unknown viruses represented the vast majority of the dominant populations, while the composition of known viruses, such as pelagiphage and cyanophage, appeared to be relatively consistent across a wide range of salinity gradients and in different seasons. A difference between estuarine and ocean viromes was reflected by the proportions of Myoviridae, Podoviridae, Siphoviridae, Phycodnaviridae, and a few well-studied virus representatives. The difference in viral community between the Delaware Bay and Chesapeake Bay is significantly more pronounced than the difference caused by temperature or salinity, indicating strong local profiles caused by the unique ecology of each estuary. Interestingly, a viral contig similar to phages infecting Acinetobacter baumannii (“Iraqibacter”) was found to be highly abundant in the Delaware Bay but not in the Chesapeake Bay, the source of which is yet to be identified. Highly abundant viruses in both estuaries have close hits to viral sequences derived from the marine single-cell genomes or long-read single-molecule sequencing, suggesting that important viruses are still waiting to be discovered in the estuarine environment.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Oxidation kinetics and microstructure evolution of high Mn stainless-steel alloy in CO 2 at 700 °C

Oxidation kinetics and scale formation were examined in 21–2N Stainless Steel alloys in a CO 2 environment at 700 °C. Several characterization techniques were used to identify the morphology, crystallographic structure, and chemical composition of the oxide scale formation during exposures up to 1925 h. High manganese content played an important role in homogenous oxide scale formation of Mn 3 O 4 and MnCr 2 O 4 at the scale/gas and scale/alloy interfaces and as an FCC stabilizer in the alloy. Depletion of Mn resulted in an FCC to BCC phase transformation at the scale/alloy interface. No carburization was observed, indicating that the oxide layer is preventing carbon uptake.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Tailoring the Radionuclide Encapsulation and Surface Chemistry of La(223Ra)VO4 Nanoparticles for Targeted Alpha Therapy

The development of targeted alpha therapy (TAT) as a viable cancer treatment requires innovative solutions to challenges associated with radionuclide retention to enhance local tumor cytotoxicity and to minimize off-target effects. Nanoparticles (NPs) with high encapsulation and high retention of radionuclides have shown potential in overcoming these issues. This article shows the influence of pH on the structure of lanthanum vanadate (LaVO4) NPs and its impact on the radiochemical yield of 223Ra and subsequent retention of its decay daughters, 211Pb and 211Bi. An acidic pH (4.9) results in a high fraction of La(223Ra)VO4 NPs with tetragonal structure (44.6–66.1%) and a 223Ra radiochemical yield <40%. Adjusting the pH to 11 yields >80% of La(223Ra)VO4 NPs with monoclinic structure and increases the 223Ra radiochemical yield >85%. The leakage of decay daughters from La(223Ra)VO4 NPs (pH 11) was <5% and <0.5% when exposed to deionized water and phosphate-buffered saline, respectively. Altering the surface chemistry of La(223Ra)VO4 NPs with carboxylate and phosphate compounds resulted in a threefold decrease in hydrodynamic diameter and a 223Ra radiochemical yield between 74.7% and 99.6%. These results show the importance of tailoring the synthesis parameters and surface chemistry of LaVO4 NPs to obtain high encapsulation and retention of radionuclides.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Identifying Potential Geochemical and Microbial Impacts of Hydrogen Storage in a Deep Saline Aquifer

Hydrogen is valuable commodity and a promising energy carrier for variable energy production. Storage of hydrogen may occur through injection of hydrogen or a hydrogen/methane gas blend in subsurface reservoirs. However, the geochemical and biological reactions that may impact the stored hydrogen are not yet understood. Therefore, we collected samples from a deep storage aquifer located in the St. Peter Formation in southern Illinois. The reservoir material was primarily quartz with sulphur and iron deposits, while the major constituents of the fluid were chloride and sulphate. 16S rRNA gene amplicon sequencing revealed a low biomass microbial community that contained no obvious hydrogen-consuming bacteria. Next, we enriched a field sample to increase the biomass and completed a metagenomic analysis, finding a low number of genes present that are associated with hydrogen consumption. Then, we completed a series of reactor experiments under reservoir conditions with 15% H2/85% CH4 gas simulating a short-term hydrogen storage, high withdrawal scenario. We found minimal changes in the geochemistry or microbiology for the reactor experiments. This work suggests that short-term storage may be highly successful, although significant additional work needs to be completed in order to accurately evaluate the risks associated with long-term hydrogen storage scenarios. It is essential we continue to expand our understanding of the dynamics present in saline aquifers and provide new insights into how hydrogen storage may impact underground geological storage environments.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Selecting representative geological realizations to model subsurface CO 2 storage under uncertainty

Carbon capture and storage (CCS) is one of the quickest and most effective solutions for reducing carbon emissions. The majority of subsurface storage occurs in saline aquifers, for which geological information is lacking which in turn results in geological uncertainty. To evaluate uncertainty in CO 2 injection projections, the use of multiple geological realizations (GRs) has been practiced very commonly. In this approach, hundreds or thousands of high-resolution GRs is used that quickly becomes computationally expensive. This issue can be addressed with representative geological realizations (RGRs) that preserve the uncertainty domain of the ensemble GRs. Here, in this study, we propose the use of unsupervised machine learning (UML) frameworks, including dissimilarity measurement, dimensionality reduction, clustering and sampling algorithms ta select a predetermined number of RGRs. We compare the simulation outputs of the RGR sets and the ensemble using the Kolmogorov–Smirnov (KS) test to select the best UML. The UML frameworks and their associated selection processes are evaluated using a saline aquifer with a single CO 2 injection well and 200 GRs with varying uncertain petrophysical characteristics. The best UML framework is selected to use only 5% of the GRs while maintaining the uncertainty domain of the ensemble GRs. In addition, the best UML framework is tested using a saline aquifer with three CO 2 injection wells and varied GRs. The results show that our proposed UML framework can be used to choose RGRs, capturing the whole uncertainty domain. Our approach leads to a significant reduction in the computational cost associated with scenario testing, decision-making, and development planning for CO 2 storage sites under geological uncertainty.

58 GEOSCIENCES↗
DOE OSTI2020

Causal Interactions between Southern Ocean Polynyas and High-Latitude Atmosphere–Ocean Variability

Abstract Weddell Sea open-ocean polynyas have been observed to occasionally release heat from the deep ocean to the atmosphere, indicating that their sporadic appearances may be an important feature of high-latitude atmosphere–ocean variability. Yet, observations of the phenomenon are sparse and many standard-resolution models represent these features poorly, if at all. We use a fully coupled, synoptic-scale preindustrial control simulation of the Energy Exascale Earth System Model (E3SMv0-HR) to effectively simulate open-ocean polynyas and investigate their role in the climate system. Our approach employs statistical tests of Granger causality to diagnose local and remote drivers of, and responses to, polynya heat loss on interannual to decadal time scales. First, we find that polynya heat loss Granger causes a persistent increase in surface air temperature over the Weddell Sea, strengthening the local cyclonic wind circulation. Along with responding to polynyas, atmospheric conditions also facilitate their development. When the Southern Ocean experiences a rapid poleward shift in the circumpolar westerlies following a prolonged negative phase of the southern annular mode (SAM), Weddell Sea salinity increases, promoting density destratification and convection in the water column. Finally, we find that the reduction of surface heat fluxes during periods of full ice cover is not fully compensated by ocean heat transport into the high latitudes. This imbalance leads to a buildup of ocean heat content that supplies polynya heat loss. These results disentangle the complex, coupled climate processes that both enable the polynya’s existence and respond to it, providing insights to improve the representation of these highly episodic sea ice features in climate models.

Kaufman, Zachary S.↗
DOE OSTI2024

Basin-scale study of CO 2 storage in stacked sequence of geological formations

Commercial scale decarbonization through carbon capture and storage may likely involve many CO 2 storage projects located in close proximity. The close proximity could raise concerns over caprock integrity associated with reservoir pressure buildup and interference among adjacent projects. Commercial-scale injection will also require large prospective CO 2 storage resource and high injectivity in the targeted storage formations. To accommodate the need for both large resource and high injectivity, project operators could consider injecting CO 2 into a stacked sequence of formations. This analysis investigates the benefits of injecting CO 2 into a vertically stacked sequence of saline formations, over injecting the same amount of CO 2 into a single saline formation, in addressing these challenges. Our analysis shows that injecting into the stacked sequence mitigates the extent of pressure buildup among the stacked formations, while still achieving the same or greater target CO 2 storage volumes. Among cases modeled, the resulting pressure buildup front is most reduced when each storage site distributes injection volumes over several wells, each of which injects a portion of the total CO 2 mass across the stacked sequence. This favorable case not only results in the smallest CO 2 aerial footprint, but also shows the largest reduction in the pressure buildup at the top of perforation at the injection wells (upwards of approximately 46% compared to the single-formation storage), the result of which is crucial to maintain caprock integrity. This analysis provides insights into required decision-making when considering multi-project deployment in a shared basin.

42 ENGINEERING↗
DOE OSTI2021

Empirical prediction of saline water atomization pressure loss and spray phase change using local flow pressure analysis

A pressure analysis technique was developed to obtain spray spatial evaporation profile in a thermal desalination process. The technique can replace temperature-based evaporation measurement methods that are challenged by liquid-phase interference. It also provides an alternative to optical methods with high cost and complexity. Fundamental analysis was developed to determine local humidity ratios from changes in local static and dynamic pressures. The analysis was applied to data obtained from an external mixing air-assist atomizer. An empirical model was developed for the pressure loss in atomization process and was used in the analysis of humidity ratio. The results were used to develop empirical correlations for local humidity ratio in spray mediums using inlet conditions. Utilizing inlet conditions to predict evaporation profiles is an important contribution as it eliminates the need to take local spray measurements. Obtaining local data is often difficult and expensive; Our method and correlation circumvent the need for that. Finally, the correlations presented in this paper apply to saline water sprays with total dissolved salt of 0-10 wt%. The salinity-specific correlations are accurate to within ±10% of experimental data. The individual models were aggregated into a unified correlation for salinities within 0-10 wt%. The unified correlation is accurate to within ±18% of experimental data.

42 ENGINEERING↗
DOE OSTI2026

Assessing the Accuracy of Property Model Predictions for Cost Optimization of Desalination Technologies

Accurate modeling of seawater thermophysical and thermodynamic properties is critical for optimizing desalination processes. This study compares three seawater property models, a Reaktoro multicomponent model, the thermophysical seawater properties library from the Massachusetts Institute of Technology, and a simplified sodium chloride model, in the context of levelized cost of water (LCOW) minimization for reverse osmosis (RO) and mechanical vapor compression systems. Process simulations and cost optimizations reveal that although all three models yield comparable LCOW and specific energy consumption (SEC) estimates under baseline conditions, deviations among their predictions increase with salinity. Relative differences in LCOW and SEC reach up to 6% and 8%, respectively. RO results show greater variability due to differences in osmotic pressure predictions, which affect pressure constraints at high recoveries. Computational performance varies substantially; specifically, Reaktoro simulations are up to 28 times slower than empirical models due to their detailed equilibrium calculations. These results suggest that empirical models offer acceptable accuracy for routine desalination process design, while Reaktoro provides advantages in scenarios requiring detailed speciation, such as scaling or pH adjustment studies. These findings underscore the importance of selecting appropriate property models based on the modeling objective of desalination applications and motivate future work integrating thermodynamic rigor with empirical efficiency.

Physical and chemical properties↗
DOE OSTI2021

Propagation of the 2014–2016 Northeast Pacific Marine Heatwave Through the Salish Sea

Effects and impacts of the Northeast Pacific marine heatwave of 2014–2016 on the inner coastal estuarine waters of the Salish Sea were examined using a combination of monitoring data and an established three-dimensional hydrodynamic and biogeochemical model of the region. The anomalous high temperatures reached the U.S. Pacific Northwest continental shelf toward the end of 2014 and primarily entered the Salish Sea waters through an existing strong estuarine exchange. Elevated temperatures up to + 2.3°C were observed at the monitoring stations throughout 2015 and 2016 relative to 2013 before dissipating in 2017. The hydrodynamic and biogeochemical responses to this circulating high-temperature event were examined using the Salish Sea Model over a 5-year window from 2013 to 2017. Responses of conventional water-quality indicator variables, such as temperature and salinity, nutrients and phytoplankton, zooplankton, dissolved oxygen, and pH, were evaluated relative to a baseline without the marine heatwave forcing. The simulation results relative to 2014 show an increase in biological activity (+14%, and 6% Δ phytoplankton biomass, respectively) during the peak heatwave year 2015 and 2016 propagating toward higher zooplankton biomass (+14%, +18% Δ mesozooplankton biomass). However, sensitivity tests show that this increase was a direct result of higher freshwater and associated nutrient loads accompanied by stronger estuarine exchange with the Pacific Ocean rather than warming due to the heatwave. Strong vertical circulation and mixing provided mitigation with only ≈+0.6°C domain-wide annual average temperature increase within Salish Sea, and served as a physical buffer to keep waters cooler relative to the continental shelf during the marine heatwave.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

An Improved Model For Determining Salinity Recharge Time for Deep Borehole Disposal - 20405

In a previous publication (K. P. Travis, D. Burley and F. G. F. Gibb, WM2017 Conference, Phoenix Arizona paper no. 17480) we introduced a numerical model to estimate the time it would take for a pressure perturbation to subside following its creation from the construction of a deep geological borehole in water-saturated rock. The model was based on the notion of a point source of momentum - a solution of the time-dependent pressure-diffusion equation. Using the model, we estimated that it would take on the order of 10 k years for physical equilibrium to become re-established following the sinking of a 5 km borehole in granite. The significance of such a model is that it places an upper bound on the lifetime required of a borehole sealing system - a necessary input to a borehole post-closure safety case assessment. No engineered sealing system has ever been devised which is capable of retaining its sealing properties for 10 half-lives of long-lived radioisotopes in spent fuel or high-level waste. One of the key advantages of disposing of nuclear waste via Deep Borehole Disposal (DBD) is the natural sealing provided by density stratified groundwater. Upon sinking of a borehole, and subsequent filling with fresh water, brine or drilling mud, this natural barrier may be temporarily damaged. Over time, fresh brine from the far-field will flow towards or away from the hole (driven by a pressure gradient) and will eventually re-establish the original salinity gradient. It follows that the engineered seals need last only as long as the time required for this salinity gradient to reset itself. One of the limitations of our previous model was the use of a static boundary condition on the borehole wall. The model used a boundary pressure which varied quadratically with depth (arising from differences between the pressure of a column of fresh water in the borehole and that of a column of brine in the host rock). However as brine replaces fresh water in the borehole (driven by a pressure gradient), the boundary function must change with time. We now introduce an improved model which takes this time dependent boundary condition into account. The model also takes into account the time taken for a mixture of brine and fresh water to re-establish chemical equilibrium through the process of diffusion. The paper contains the mathematical details of our new iterative model as well as results showing the time taken to reach steady state, and concentration profiles for the components of the brine-filled borehole as a function of time together with a discussion on the implications of the results for developing a post-closure safety assessment for DBD. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

The solubility of NdPO 4 and DyPO 4 and stability of Nd and Dy chloride and hydroxyl complexes as a function of pH and salinity to 450 °C

The mobility of rare earth elements (REE) in geological systems is often controlled by the stability of monazite and xenotime, which are important hosts for the light and heavy REE. These REE phosphates constitute important resources and provide information on ore formation conditions and timing due to their uses as geothermometers and geochronometers. While the thermodynamic properties for these minerals are well-established up to high temperature and pressure, the properties for the aqueous REE complexes are not well constrained with limited information up to 300 °C. In this study, the solubility of synthetic NdPO 4 and DyPO 4 endmembers were measured in hydrothermal sub- to supercritical NaCl-bearing aqueous solutions from 350 at saturated water vapor pressure to 450 °C at 700 bar. The speciation of Nd and Dy was determined in acidic to alkaline solutions (pH 25 °C values from 2 to 10), and indicates that the hydroxyl species REE(OH) 2 + and REE(OH) 3 0 predominate at low salinity (0.01 mol/kg NaCl) with some contribution of REE chloride species REECl 2+ and REECl 2 + in acidic fluids. The REE phosphate solubility measured in these experiments is up to two orders of magnitude higher than predicted using existing thermodynamic properties from literature for aqueous species extrapolated from lower temperature data to supercritical conditions. To address this discrepancy, the thermodynamic properties of the REE aqueous species were optimized using GEMSFITS to derive the formation constants for the REE chloride (β Cl ) and hydroxyl (β OH ) complexes in the studied temperature range. This study highlights the importance of the hydroxyl species REE(OH) 2 + and REE(OH) 3 0 over a wide range of pH and temperature. As a result, the revised thermodynamic properties for Dy and Nd chloride and hydroxyl species more accurately predict the solubility of NdPO 4 and DyPO 4 and provide insight into the speciation and mobility of the light and heavy REE in hydrothermal supercritical fluids in the crust.

58 GEOSCIENCES↗