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Extraction of Mercury Utilizing 3D Printed Media-Mercury Extraction Coalescer (MEC)

This project was undertaken to address the concern of mercury species present in chemical reprocessing facilities and environmental remediation sites. Typical elemental mercury removal is performed by steam stripping. As efficient as this process is, the vaporized elemental mercury is often condensed along with acidic condensate. The acidic conditions re-dissolve the elemental mercury, transferring it back into the aqueous stream, and undoing the energy-intensive steam stripping process. This project looked to design and produce a 3D printed component to act as a mercury vapor/liquid coalescer utilizing structural and chemical features to segregate elemental mercury from an aqueous solution or process offgas and improving elemental mercury retention and removal from the recirculated condensate stream. The aim of this project is to take inspiration from nature, for example the lotus leaf, and the advantage of advanced manufacturing techniques, in this case 3D printing, to produce a functional solution to a serious environmental issue, the accumulation of elemental mercury in aqueous environments.

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Extraction of Mercury Utilizing 3D Printed Media - Mercury Extraction Coalescer (MEC)

Mercury is a persistent environmental hazard that is strictly regulated. The design of a 3D printed coalescer was proposed to facilitate segregation and/or adsorption of elemental mercury from aqueous solutions. 3D printing techniques were employed to generate designed surfaces and internal geometries that would otherwise be very difficult to near impossible through traditional manufacturing processes. The proposed coalescer was designed to take advantage of advancements in 3D printing to incorporate surface sub-structures and material compositions targeted specifically at mercury adsorption. The initial phase of research targeted the design of physical structures that could assist with adsorption or segregation of mercury from acidic condensate, rendering it isolated and preventing recirculation back into the chemical process, as well as implementation into standard environmental remediation techniques for contaminated aqueous solutions. Future work was to focus on formulating reactive coalescers to improve chemisorption along with physisorption.

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Extraction of Mercury Utilizing 3D Printed Media – Mercury Extraction Coalescer (MEC) (Revision 1)

This project was undertaken to address the concern of mercury species present in chemical reprocessing facilities and environmental remediation sites. Typical elemental mercury removal is performed by steam stripping. As efficient as this process is, the vaporized elemental mercury is often condensed along with acidic condensate. The acidic conditions re­-dissolve the elemental mercury, transferring it back into the aqueous stream, and undoing the energy-intensive steam stripping process. This project looked to design and produce a 3D printed component to act as a mercury vapor/liquid coalescer utilizing structural and chemical features to segregate elemental mercury from an aqueous solution or process offgas and improving elemental mercury retention and removal from the recirculated condensate stream.

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Extraction of Mercury Utilizing 3D Printed Media - Mercury Extraction Coalescer (MEC) (Revision 1)

The presence of mercury in environmental or industrial settings presents a number of issues from bio-accumulation to production of toxic by-products. The primary objective of this project was the development of a 3D printed component designed to act as a coalescing filter for the removal or segregation of elemental mercury from aqueous streams. The use of 3D printing allows for the design and integration of surface microstructures and internal geometries that could be difficult if not impossible to achieve through traditional manufacturing techniques. The initial phase of testing focused on the integration of 3D printed components into both environmental remediation testing (university subcontracted testing) and simulations of high-level nuclear waste processing (SRNL). Structures ranged from simple torturous paths that provided regions where the elemental mercury could settle out of the recirculation process to micro-structured frits that have increased surface area for aid in droplet coalescence and surface adsorption.

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Comprehensive Database of Environmental Mitigations Extracted from FERC-Licensed Hydropower Projects Using Artificial Intelligence Techniques, 1998-2023

This dataset provides a comprehensive inventory of environmental mitigation measures required by Federal Energy Regulatory Commission (FERC) licensed hydropower facilities from 461 licenses that were issued from 1998 to 2023. These licenses constitute 446 of the 1015 FERC projects that were active at the end of 2023. 17,612 mentions of environmental mitigations were identified and categorized in 128 unique categories. Mitigations were identified using a Natural Language Processing (NLP) approach, specifically with a Bidirectional Encoder Representations from Transformer (BERT) model. Model-derived results were then reviewed and updated by a subject matter expert as needed. This dataset introduces important enhancements to previous efforts to inventory environmental mitigations, such as including associated license text for each mitigation, tracking the number of instances a mitigation was identified within a license, and providing improved location information. These enhancements significantly expand the dataset's utility, offering greater analytical capabilities and ensuring reproducibility. The dataset is downloadable as a zip file containing the metadata and dataset files.

Ruggles, Thomas [Oak Ridge National Laboratory (OR↗

Extracting the distribution amplitude of light pseudoscalar mesons using the HOPE method

The pseudoscalar meson light-cone distribution amplitudes (LCDAs) are essential non-perturbative inputs for a range of high-energy exclusive processes in quantum chromodynamics. In this proceedings, progress towards a determination of the low Mellin moments of the pion and kaon LCDAs by the HOPE Collaboration is reported.

Chang, Alex [National Yang Ming Chiao Tung Univers↗

Brine Extraction and Treatment Strategies to Enhance Pressure Management and Control of CO 2 Plumes in Deep Geologic Formations

The overall goal of the this project is to develop and validate pressure management and carbon dioxide (CO 2 ) plume control strategies that can address technical and economic barriers to commercial deployment of CO 2 storage technologies, based on computational and field demonstration work at the Archer Daniels Midland Company (ADM) facility where the Illinois Basin–Decatur Project (IBDP) and the Illinois-Industrial Carbon Capture and Storage (IL-ICCS) projects are located. To accomplish the overall goal, the ISGS designed a brine extraction storage test (BEST) that could be completed in two phases. The goal of BEST Phase I was to evaluate the feasibilities of extraction well(s) placement, the brine extraction to CO 2 injection rate ratio, extraction well completion, and brine treatment and handling. The goal of BEST Phase II would be to validate the brine extraction and treatment options deemed feasible in Phase I by (1) demonstrating the efficacy of brine extraction (BE) in managing pressure (i.e., formation) and the CO 2 plume, and (2) demonstrating treatment of extracted brine with high total dissolved solids (TDS; >200,000 mg/L) using multiple advanced treatment technologies. This report details work done in Phase I. Several brine extraction and treatment scenarios were tested, simulated, and analyzed for their effectiveness in extracting brine. Initially a vertical well was studied; however, geologic modeling, reservoir modeling, and the existing facility and wellbore infrastructure dictated that the location of a vertical brine extraction well was limited to an area with no existing monitoring wells and where the well would be in relative proximity to an existing CO 2 plume. Consequently, a vertical well was excluded, and a horizontal brine extraction well placed above the existing CO 2 plume near two existing wells was studied. The horizontal well option allows the project to leverage the availability of cased-hole logs and cross-well tomography to monitor CO 2 saturation and plume distribution, respectively. Because of the proximity of the horizontal well option to two existing wells, no additional monitoring well (or caprock penetration) is required. The recommended brine extraction pilot design options are (1) a horizontal extraction well at the base of the Middle Mt. Simon, which is 350–520 ft (107–158 m) above the CO 2 plume at CCS#1 and VW#1; or (2) a vertical extraction well 0.5 mi (0.8 km) from CCS#2 in a direction approximately southeast of CCS#2, perpendicular to the direction of high hydraulic connectivity. A horizontal extraction well has advantages over a vertical extraction well, including less risk of drilling into an existing CO 2 plume and it can be located between two other wells that can be used for monitoring. Thus, because the two existing wells can serve as monitoring wells, it eliminates the need for a third verification well and allows for a lower extraction rate to control the CO 2 plume and pressure. Managing pressure and the CO 2 plume distribution via brine extraction creates the obvious and important challenge of handling and treating the extracted brine. There were three options for brine disposal: (1) underground injection control (UIC) disposal well, (2) brine treatment and industrial use, and (3) brine pretreatment and discharge into municipal wastewater system. The primary design elements were budget and permitting requirements. The disposal well would be a vertical well drilled and completed into the Potosi Dolomite. For the range of extraction rates anticipated, the cost of this well is relatively constant. The cost of brine treatment is highly depends on the extraction rate, which depends on the well orientation. If relatively high rates are required, the vertical disposal well option is more favorable; for relatively lower rates, the two brine treatment options have lower costs. Life-cycle-analysis studies on extracted brine handling options suggest that a UIC well has a lower environmental impact than brine treatment. Both brine disposal options using brine treatment require removal of suspended solids from the extracted brine. The most suitable commercially available technology and the most promising emerging and innovative technology are recommended for implementation in Phase II. Though the challenges of this project are written specific to Decatur, every CO 2 storage site considering the use of brine extraction integrated with CO 2 storage will have similar, if not identical, technical and logistical challenges.

58 GEOSCIENCES↗

Insights into water extraction and aggregation mechanisms of malonamide-alkane mixtures

Structure at the nanoscale in the organic phase of liquid–liquid extraction systems is often tied to separation performance. However, the weak interactions that drive extractant assembly lead to poorly defined structures that are challenging to identify. Here, in this work, we investigate the mechanism of water extraction for a malonamide extractant commonly applied to f-element separations. We measure extractant concentration fluctuations in the organic phase with small angle X-ray scattering (SAXS) before and after contact with water at fine increments of extractant concentration, finding no qualitative changes upon water uptake that might suggest significant nanoscopic reorganization of the solution. The critical composition for maximum fluctuation intensity is consistent with small water–extractant adducts. The extractant concentration dependence of water extraction is consistent with a power law close to unity in the low concentration regime, suggesting the formation of 1 : 1 water–extractant adducts as the primary extraction mechanism at low concentration. At higher extractant concentrations, the power law slope increases slightly, which we find is consistent with activity effects modeled using Flory–Huggins theory without introduction of additional extractant–water species. Molecular dynamics simulations are consistent with these findings. The decrease in interfacial tension with increasing extractant concentration shows a narrow plateau region, but it is not correlated with any change in fluctuation or water extraction trends, further suggesting no supramolecular organization such as reverse micellization. This study suggests that water extraction in this system is particularly simple: it relies on a single mechanism at all extractant concentrations, and only slightly enhances the concentration fluctuations characteristic of the dry binary extractant/diluent mixture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Disulfonamide Ligands as f-Element Extractants from Alkaline High-Level Waste

Almost 100 million gallons of high level waste (HLW) has been generated from defense reprocessing programs to support nuclear weapons production. HLW is currently stored at the Hanford and Savannah River Sites (SRS) [1]. It contains radioactive components, such as {sup 137}Cs, {sup 99}Tc and {sup 90}Sr, as well as large amounts of non-radioactive species, including solvated cations and insoluble metal hydroxides. HLW has high concentration of soluble hydroxides ([OH{sup -}] = 2 M at SRS [2]), complexing inorganic anions ([NO{sub 3}{sup -}] ∼ 0.65 - 3.7 M at SRS [2]) and a high ionic strength. Even though the majority of actinide component in alkaline HLW is precipitated, studies of An(III) and Ln(III) complexation in highly alkaline solutions in the presence of high nitrate concentrations have showed that soluble nitrate complexes can be formed [3]. The current treatment of HLW at SRS currently consists of two processes: The Actinide Removal Process (ARP) and the Next-Generation Caustic-Side Solvent Extraction process (NG-CSSX). Strontium and actinides are removed by sorption on monosodium titanate through the Actinide Removal Process (ARP) commonly referred to as the alpha-strike step [4]. Then, cesium is selectively extracted from the alkaline media via the Caustic-Side Solvent Extraction (CSSX) process [5]. The CSSX solvent consists of a calix[4]arene-crown-6 extractant dissolved in an inert hydrocarbon matrix containing i) a solvent modifier (alkylphenoxy alcohol) which increases extractant solubility and prevents third phase formation, and ii) a suppressor (trioctylamine or guanidine) - that mitigates surfactant effects. The CSSX process removes {sup 137}Cs selectively and rapidly, yet the post- CSSX aqueous stream may still contain high amounts of An, thus requiring a second ARP treatment (referred to as 'alpha-finishing') for some tanks. Despite the success of the ARP process in removing Sr and An, it often represents the kinetic bottleneck of integrated processing, as it is slower than solvent extraction. Understanding the complexation of actinides by organic ligands that are compatible with the CSSX process could eventually lead to a combined caustic-side Cs/Sr/actinide extraction process with better economics due to a reduced amount of monosodium titanate and/or a shorter required contact time with titanate during ARP. This would ensure a low-activity waste (LAW) stream with no actinides without additional ARP processing post-CSSX. Disulfonamides were studied for extraction of Sm(III) from alkaline aqueous media of pH 10-14 into dichloromethane. Up to 82% of Sm(III) was extracted from solutions of pH 12.5 -13.5 and up to 84% from solutions of pH 10.5 - 11.5. These results show some resemblance with Am extraction results by calixarene ligands previously reported [10]. Kinetic studies demonstrated that even 5 min is enough to complete stripping, whereas extraction is time-limiting process and requires up to 20 h for efficient removal of Sm(III) from alkaline aqueous media. Determination of composition of complexes in solution after extraction by the equilibrium shift method showed a 1:1 Sm(III):dsa-2 complexation ratio for the extracted species.

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Humic Substances Extracted by Alkali Are Invalid Proxies for the Dynamics and Functions of Organic Matter in Terrestrial and Aquatic Ecosystems

The conceptual rigor of using organic materials extracted from soil by alkali, called humic substances, as proxies for soil organic matter has been questioned for almost 180 years. However, the humic substances paradigm, i.e., the understanding that alkali-extracted humic substances are newly synthesized materials with unique properties that are distinct from non-humic organic matter, continues to be propagated throughout the literature. Here, we revisit the mechanistic background of the extraction process to show that alkaline extraction is unable to discriminate for the chemical history of a compound. For this reason, alkaline extraction cannot distinguish between (i) materials that have undergone secondary synthesis or humification (“humic” substances), and (ii) materials that are decorated with ionizable functional groups for other reasons, such as oxidative depolymerization (“non-humic” substances). While this mechanistic consideration alone renders invalid a distinction between humic substances and non-humic substances based on alkaline extraction, we further show that the evidence available to date does not support the assumption that processes of secondary synthesis create quantitatively significant proportions of “chemically reactive, yet recalcitrant” materials in natural environments. Any definition of humic substances that invokes both alkaline extraction and secondary synthesis is thus flawed on at least two accounts: (i) alkaline extraction is unable to achieve its purpose of separating humic from non-humic substances, and (ii) the assertion that the extracted materials have unique molecular properties as a consequence of secondary synthesis cannot be proven because alkaline extraction cannot separate materials created by secondary synthesis from other, ionizable organic compounds. Finally, we point out that since the definition of humic substances is tied to the alkaline-extraction procedure, neither the existence of operationally defined humic substances in the environment nor their chemical integrity during the course of alkaline extraction can be independently verified. We conclude that organic materials extracted by alkali require appropriate nomenclature and rigorous definition to merit consideration in teaching, research, and application.

54 ENVIRONMENTAL SCIENCES↗