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At least 325 records · Page 18

On the Mechanism of the Steady-State Gamma Radiolysis-Induced Scissions of the Phenyl-Vinyl Polyester-Based Resins

The major societal problem of polymeric waste necessitates new approaches to break down especially challenging discarded waste streams. Gamma radiation was utilized in conjunction with varying solvent environments in an attempt to discern the efficacy of radiolysis as a tool for the deliberate degradation of model network polyesters. Our EPR results demonstrated that gamma radiolysis of neat resin and in the presence of four widely used solvents induces glycosidic scissions on the backbone of the polyester chains. EPR results clearly show the formation of alkoxy radicals and C-centered radicals as primary intermediate radiolytic products. Despite the protective role of the phenyl groups on the backbone of the radiation-induced polyester chains, the radiolytic-glycosidic scissions predominate. Among the following three solvents used in this study (water, isopropyl alcohol, and dichloromethane), the highest radiolytic yield of glycosidic scission was achieved using water. The •OH radicals produced in the radiolysis of phenyl unsaturated polyester aqueous suspensions very rapidly abstract H atoms from the methylene group, which is followed by a very rapid glycosidic scission. The lowest glycosidic yield was found in the dichloromethane solutions of these polyester resins due to scavenging by the fast electron capture reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Iodine Capture with Copper-Electroplated Nickel Foams

This work explores the use of Ni0 foam scaffolds for Cu0 coatings for use as sorbents for iodine. The Cu0 electroplating was performed from aqueous copper(II) sulfate (CuSO4) solutions under different conditions to achieve a range of Cu0-layer thicknesses (4.89 ± 1.05 μm–57.32 ± 3.95 μm) with 900 A·m–2 current densities and coating times of 15–180 min. The thickest coatings resulted in Cu0-plated Ni0 foams with >89 mass % Cu0 in the final product. Iodine capture experiments showed very high Cu0 utilizations of 91.9–97.3 mass % at iodine loadings of 839–1774 mg·g–1 through the formation of CuI (marshite; space group F-43m). No evidence was found of iodine reactions taking place with the Ni0 scaffold, so it remained in iodine-loaded Cu-electroplated Ni foams as structural support to provide mechanical rigidity to the foams during the iodine loading process. Hot pressing of these materials can be used to create a CuI/Ni ceramic-metal composite waste form for disposal as demonstrated with spark plasma sintering.

Riley, Brian [Pacific Northwest National Laborator↗

Enabling Microscale Processing: Combined Raman and Absorbance Spectroscopy for Microfluidic On-Line Monitoring

Microfluidics have many potential applications including characterization of chemical processes on a reduced scale, spanning the study of reaction kinetics using on-chip liquid–liquid extractions, sample pretreatment to simplify off-chip analysis, and for portable spectroscopic analyses. The use of in situ characterization of process streams from laboratory-scale and microscale experiments on the same chemical system can provide comprehensive understanding and in-depth analysis of any similarities or differences between process conditions at different scales. A well-characterized extraction of Nd(NO 3 ) 3 from an aqueous phase of varying NO 3– (aq) concentration with tributyl phosphate (TBP) in dodecane was the focus of this microscale study and was compared to an earlier laboratory-scale study utilizing counter current extraction equipment. Here, we verify that this same extraction process can be followed on the microscale using spectroscopic methods adapted for microfluidic measurement. Concentration of Nd (based on UV–vis) and nitrate (based on Raman) was chemometrically measured during the flow experiment, and resulting data were used to determine the distribution ratio for Nd. Extraction distributions measured on the microscale were compared favorably with those determined on the laboratory scale in the earlier study. Both micro-Raman and micro-UV–vis spectroscopy can be used to determine fundamental parameters with significantly reduced sample size as compared to traditional laboratory-scale approaches. This leads naturally to time, cost, and waste reductions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion Pairing Mediates Molecular Organization Across Liquid/Liquid Interfaces

Liquid/liquid interfaces play a central role in scientific fields ranging from nanomaterial synthesis and soft matter electronics to nuclear waste remediation and chemical separations. This diversity of functions arises from an interface’s ability to respond to changing conditions in its neighboring bulk phases. Understanding what drives this interfacial flexibility can provide novel avenues for designing new functional interfaces. However, limiting this progress is an inadequate understanding of the subtle intermolecular and interphase interactions taking place at the molecular level. Here, we use surface-specific vibrational sum frequency generation spectroscopy combined with atomistic molecular dynamics simulations to investigate the self-assembly and structure of model ionic oligomers consisting of an oligodimethylsiloxane (ODMS) tail covalently attached to a positively charged methyl imidazolium (MIM + ) head group at buried oil/aqueous interfaces. We show how the presence of seemingly innocuous salts can impart dramatic changes to the ODMS tail conformations in the oil phase via specific ion effects and ion-pairing interactions taking place in the aqueous phase. These specific ion interactions are shown to drive enhanced amphiphile adsorption, induce morphological changes, and disrupt emergent hydrogen-bonding structures at the interface. Tuning these interactions allows for independent control over the oligomer structure in the oil phase versus interfacial population changes and represents key mechanistic insight that is needed to control chemical reactions at liquid/liquid interfaces.

36 MATERIALS SCIENCE↗

Enhanced, continuous, liquid-liquid extraction and in-situ separation of volatile fatty acids from fermentation broth

In 2018 alone, the US landfilled 35.3 million tons of food waste, about 24% of the total landfilled mass. In addition to the negative impacts landfills have demonstrated on the environment and human health, some states have begun to outlaw or dissuade the disposal of food waste and sewage sludge into landfills altogether. An urgent need has thus been created for the development of digestion processes like anaerobic digestion (AD) and arrested methanogenesis (AM) to convert food waste into valuable chemical products. Unfortunately, the buildup of volatile fatty acids (VFAs) during these processes eventually halts the reaction, and energy efficient methodologies for VFA removal are critical for the operation of fermenters. Additionally, VFAs themselves can serve as valuable chemical precursors, and recently AD processes have been modified to increase VFA production during fermentation. However, even with significant research over the past three decades, the separation of VFAs from the fermenter broth has remained expensive. Moreover, the separation of these VFAs from the fermenter broth may cost up to 50% of the entire process budget, hindering the widespread commercial adoption of AD and AM. Here we present a novel liquid-liquid extraction process termed CLEANS (Continuous Liquid-liquid Extraction And iN-situ Separation) as a highly efficient method for continuously separating VFAs from a real fermentation broth solely under gravity. Our optimized process (using an aqueous broth feed pH of 2.5, tri-noctylamine as an extractant, and a 10:1 ratio of aqueous broth to organic extractant), achieved a VFA distribution constant K D = 44.5 ± 7.9, a single-pass recovery = 81.3 ± 2.5%, and an extraction factor = 8.1 ± 0.3. These KD values are over an order of magnitude higher than what has been previously reported for comparable processes. A high aqueous-to-organic flowrate ratio, enabled for the first time by CLEANS, was found to be particularly crucial for achieving optimal extraction. Our separation process demonstrates excellent reproducibility and potential for scalability. The economic and environmental implications of this work are briefly discussed.

42 ENGINEERING↗

High Solids Loading Aqueous Slurry Formation of Corn Stover Before Pretreatment in a Fed-batch Bioreactor

With the increase on population the world will depend on renewable sources to meet the increasingly energy needs. Use of lignocellulosic biomass as a renewable source has been proven efficient for conversion to cellulosic ethanol and capable of contributing to achieve the threshold on energy demand while reducing greenhouse gases in 90% when compared with fossil fuels (Wang et al., 2007, 2012). However, the processing of biomass encounters limitations in feeding and flow within biorefineries due to the system plugging by compaction and slurry high yield stress, preventing transport of biomass materials and in some cases unexpected plant shutdowns that results in high operational costs (dos Santos et al., 2021; Ximenes et al., 2021). Different solutions for biomass handling and slurry formation from densified materials like pellets have been studied. Cellulosic biomass residues are typically processed in pretreatment reactors to which acid or base is added (Humbird et al., 2002). Other pretreatments such as liquid hot water (LHW) and steam explosion that act without the addition of chemicals use pressures above the saturation vapor of water, to disrupt biomass structure (Ruiz et al., 2021). Although these methods are widely known, the use of pretreatments like acid digestion and LHW present challenges like waste disposal and could be energy inefficient (Mosier et al., 2005). Alternatively other approaches like enzymatic liquefaction have been applied for biomass transformation into slurries with promising results and without the use of pretreatments (dos Santos et al., 2021). Nevertheless, enzymatic liquefaction implementation faces difficulties due to the recalcitrant properties of biomass, its variability, and the release of enzyme inhibitors. While it has been proven that chemical composition properties in biomass have effects on enzyme inhibition (Huang et al., 2022; Kim et al., 2011; Zhai et al., 2018), hindering the efficiency of the liquefaction, not ample research has been conducted in understanding the physical properties as particle size, porosity, water adsorption retention and their effect in the ability to form a slurry at high solids concentration (Yan et al., 2020). In order to improve lignocellulosic biomass handling and formation of biomass slurries, enzyme assisted liquefaction for slurry creation from corn stover at solids loadings up to 30% is reported in this work. Two different kinds of biomass (pelleted corn stover and cobs) were liquefied in a fed-batch process using commercial enzymes Celluclast 1.5L or Ctec-2 at 1FPU or 3 FPU per gram of dry solids in 10 mM sodium citrate buffer solution (pH 4.8). Pellets were fed into a 1 L stirred bioreactor according to a predefined fed-batch protocol over the first 5 hours until reaching 30% of solids loading. After 6, 24 and 96 hours, samples were taken and characterized with respect to their sugar composition, rheology and water absorption. Successful slurry creation with dramatically reduced yield stress was achieved for corn stover for both assessed enzymes. Yield stresses of 178±7 Pa (3 FPU, Celluclast 1.5L) and 79±6 Pa (3 FPU, Ctec-2) were measured for corn stover at 24 hours, compared to 6,000 Pa for samples without enzyme. Yield stress was 155± 29 Pa (3FPU, Ctec-2) and 257 ± 72 Pa (1 FPU, Celluclast 1.5L) for corn cobs at 24 hours. Yield stress decreased when residence time increased with an enhanced fluidity noted for higher enzyme concentrations. A profile for 6, 24 and 96h of yield stress measurements is presented.

Gutierrez, Diana↗

Ultrafiltration separation of Am(VI)-polyoxometalate from lanthanides

Partitioning of americium from lanthanides (Ln) present in used nuclear fuel plays a key role in the sustainable development of nuclear energy. This task is extremely challenging because thermodynamically stable Am(III) and Ln(III) ions have nearly identical ionic radii and coordination chemistry. Oxidization of Am(III) to Am(VI) produces AmO 2 2+ ions distinct with Ln(III) ions, which has the potential to facilitate separations in principle. However, the rapid reduction of Am(VI) back to Am(III) by radiolysis products and organic reagents required for the traditional separation protocols including solvent and solid extractions hampers practical redox-based separations. Herein, we report a nanoscale polyoxometalate (POM) cluster with a vacancy site compatible with the selective coordination of hexavalent actinides ( 238 U, 237 Np, 242 Pu and 243 Am) over trivalent lanthanides in nitric acid media. To our knowledge, this cluster is the most stable Am(VI) species in aqueous media observed so far. Ultrafiltration-based separation of nanoscale Am(VI)-POM clusters from hydrated lanthanide ions by commercially available, fine-pored membranes enables the development of a once-through americium/lanthanide separation strategy that is highly efficient and rapid, does not involve any organic components and requires minimal energy input.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Laboratory Evaluation to Increase Effectiveness of Field-Scale Soil Flushing in the Hanford 100 Areas

This laboratory study was initiated to develop an improved technical understanding of the key controlling geochemical and physical processes of mobilizing residual Cr(VI) in Hanford sediments to provide increased effectiveness in soil flushing activities planned for Hanford 100 Areas. This was accomplished by (1) quantifying Cr mass, release rate, and surface phase changes as Cr is leached from different Hanford sediments; (2) maximizing Cr leaching during soil flushing by evaluating different leach solutions and leach strategies; and (3) minimizing leaching of remaining residual Cr after soil flushing ends. To quantify geochemical controls on Cr leaching from sediments, sequential liquid extractions were used to identify aqueous, adsorbed, and solid Cr surface phases (precipitates or Cr incorporated into other phases) before and after water-saturated and unsaturated leach experiments with pH 8 artificial groundwater and with other amendment solutions. Changes in the Cr release rate from sediments were also correlated to changes in Cr surface phases. During unsaturated infiltration, water advection occurs primarily through larger pores, with less movement through smaller grain layers leading to a slower release of Cr trapped in smaller pores next to smaller grains. To quantify these physical controls on Cr leaching from sediments, 10 ft high 1-D infiltration experiments were conducted at differing leach solution application rates, and Cr leaching during application and subsequent residual water flow was quantified. Qualitative 2-D experiments were also conducted to evaluate surfactant addition to increase flow in low-permeability zones. Cr-contaminated Hanford sediments from the 100-H, 100-K, 100-D, and 200 East Areas exhibited a wide variety of leach behavior from rapid release of a small amount of Cr to fast (i.e., minutes) and slow (i.e., hours or more) release of high Cr. Sediments with low labile Cr (< 0.2 µg/g) exhibited fast Cr release but less overall release, and most (>95%) leached from the sediments within a few pore volumes in water-saturated columns. With nearly no sorption of chromate, aqueous and sorbed Cr (as chromate) were released quickly from sediment within the first few pore volumes, resulting in high leach concentrations, fast initial Cr release rates, and changes in pre- and post-leach extractions. In contrast, sediments with high labile Cr (0.2 to 20 µg/g) exhibited a combination of fast and slow Cr release due to multiple Cr surface phases contributing to Cr release from the sediment at different rates with greater overall release. This resulted in elevated Cr effluent concentrations even after dozens of pore volumes were leached. In addition, the Cr release rate decreased with increasing time during leaching. A decrease in labile Cr (aqueous Cr, adsorbed Cr, pH 5 acetate dissolved precipitates) in post-leach extractions compared to pre-leach extractions showed initial aqueous and adsorbed Cr release, followed by dissolution of high-solubility precipitates such as CaCrO 4 (if present), then slow dissolution of calcite that may contain some chromate and possibly BaCrO 4 . The labile Cr in all sediments correlated well with the Cr release rate (r 2 = 0.81). Labile Cr also correlated well with the leached mass in water-saturated columns (r 2 = 0.98), and therefore can be used for prediction of potential removal with flushing applications.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Critical review of functionalized silica sorbent strategies for selective extraction of rare earth elements from acid mine drainage

We report the ubiquitous and growing global reliance on rare earth elements (REEs) for modern technology and the need for reliable domestic sources underscore the rising trend in REE-related research. Adsorption-based methods for REE recovery from liquid waste sources are well-positioned to compete with those of solvent extraction, both because of their expected lower negative environmental impact and simpler process operations. Functionalized silica represents a rising category of low cost and stable sorbents for heavy metal and REE recovery. These materials have collectively achieved high capacity and/or high selective removal of REEs from ideal solutions and synthetic or real coal wastewater and other leachate source. These sorbents are competitive with conventional materials, such as ion exchange resins, activated carbon; and novel polymeric materials like ion-imprinted particles and metal organic frameworks (MOFs). This critical review first presents a data mining analysis for rare earth element recovery publications indexed in Web of science, highlighting changes in REE recovery research foci and confirming the sharply growing interest in functionalized silica sorbents. A detailed examination of sorbent formulation and operation strategies to selectively separate heavy (HREE), middle (MREE), and light (LREE) REEs from the aqueous sources is presented. Selectivity values for sorbents were largely calculated from available figure data and gauged the success of the associated strategies, primarily: (1) silane-grafted ligands, (2) impregnated ligands, and (3) bottom-up ligand/silica hybrids. These were often accompanied by successful co-strategies, especially bite angle control, site saturation, and selective REE elution. Recognizing the need to remove competing fouling metals to achieve purified REE “baskets,” we highlight techniques for eliminating these species from acid mine drainage (AMD) and suggest a novel adsorption-based process for purified REE extraction that could be adapted to different water systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating Polymer Properties with Different Additives for Carbon Capture and Other Applications

Anthropogenic climate change is one of this generation’s most pressing concerns, with the potential to completely alter the delicate balance we’ve struck with nature. Already, global temperatures have risen 1.29°C, leading to disrupted weather systems, extinctions, increased risks of wildfires, and sea level rise, to name a few effects. Carbon dioxide emission from the combustion of fossil fuels and other industrial activity is a large driver of this phenomenon, as it absorbs heat before it can be radiated away from Earth, trapping it. Carbon dioxide has reached unprecedented levels in our atmosphere, showing a 50% increase from preindustrial averages to a whopping 430 ppm. Thus, reducing the amount of carbon dioxide via carbon capture technology is an important endeavor that serves to benefit everyone. The Microencapsulated CO 2 Sorbent (MECS) team at Lawrence Livermore National Laboratory (LLNL) has turned to microencapsulation to approach this endeavor. Microcapsules provide an attractive approach to carbon capture, combining large surface areas for more efficient mass transfer, regenerative abilities, reduced solvent loss, and improved handling. Additionally, while existing carbon capture technology relies on industrial plants, capsules could present a modular approach to carbon capture, reducing the need for extensive physical infrastructure. The MECS team’s design consists of a polymer membrane that contains a liquid carbon sequestering sorbent, aqueous sodium carbonate. The carbon capturing reaction occurs in three distinct steps, the first of which is the dissolution of carbon dioxide into the sorbent solution and its conversion into carbonic acid (H 2 CO 3 ), shown in equations 1 and 2 respectively. Because this step hinges upon the ability of carbon dioxide to reach the solution inside the capsule, it is necessary that the microcapsule shell is permeable to carbon dioxide gas. The MECS team produces these microcapsules using the in-air droplet encapsulation apparatus (IDEA) shown in figure 1, which can produce uniform micron-scale droplets at speeds much faster than traditional single-dispersal microfluidic-based techniques. The IDEA Is 100 times faster than these current techniques and can reach up to 1000 times their speed when incorporating a multi-nozzle design. Additionally, because droplets are produced in-air via vibration, IDEA can decrease post-processing times and material waste by 99% and can fabricate microgels that are 10 to 100 times more viscous than can be produced via traditional microfluidics. While this design represents a breakthrough in the throughput, efficiency, and tunability of microcapsule production, it imposes a major constraint on the microcapsule curing process. Because microcapsule shells are crosslinked with UV light while falling 30 cm through the air, this gives them a reaction window of approximately 0.2 seconds. Thus, the system and shell formulations must be optimized such that the shells can be fully crosslinked within this very narrow window, prompting investigations into curing behavior.

36 MATERIALS SCIENCE↗

Probing elemental speciation in hydrochar produced from hydrothermal liquefaction of anaerobic digestates using quantitative X-ray diffraction

Valorization of hydrochar, a solid byproduct from hydrothermal liquefaction (HTL) of anaerobically-digested agriculture wastes (digestates), requires fundamental knowledge of elemental speciation. This study investigated the effects of reaction temperatures (320–360 °C), digestate pH (3.5–8), and digestate cellulose-to-lignin ratios (0.2–1.8) on the speciation (chemical form) and composition of organics and inorganics in hydrochars produced during hydrothermal treatment. Quantitative X-ray diffraction (XRD) method was the primary technique used to characterize hydrochars. The comprehensive XRD pattern processing including the Rietveld refinement protocols demonstrated that the organic phase was comprised of mostly crystalline monocyclic, heterocyclic, and polycyclic aromatics with diverse aliphatic and aromatic substituents, while the inorganic mineral phase consisted of calcium-phosphates, magnesium-phosphates, calcium-carbonates, and magnesium-carbonates. Further, XRD results were validated by the elemental yields of products and the distribution of chemical functionalities measured using solid-state nuclear magnetic resonance (NMR) spectroscopy. The characterization data were used to evaluate proposed mechanistic pathways using compositional analysis of biocrude and aqueous-phase coproducts. Mechanistic pathways developed in the study suggested that benzoic acids, phenols, benzaldehydes, phenolic aldehydes, α-dicarbonyls, and α-hydroxycarbonyls were responsible for the precipitation of organics through various reactions depending on operating conditions. Meanwhile, the formation of inorganic compounds appeared to be consistently represented by reactions including dehydration, hydrolysis, endergonic reduction, and structure rearrangement of native minerals in the digestates. This study provides basic knowledge needed to create and assess potential elemental speciation pathways. In addition, the results of the study facilitate the specification of process conditions to optimize targeted utilization routes of hydrochar for more economically-feasible and sustainable HTL processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

National Energy Water Treatment & Speciation (NEWTS): A Water & Critical Mineral Database and Dashboard

The scarcity of water resources, the need for beneficial water reuse, and the challenges of wastewater treatment are becoming increasingly pressing in economic, social, and environmental domains. Addressing these concerns requires effective treatment strategies to manage wastewater streams and tackle environmental and economic issues. Furthermore, the recovery of critical minerals from the waste streams associated with energy production holds the promise of offsetting treatment costs and securing local sources of valuable minerals. However, relevant data on these waste streams are dispersed and challenging to locate. The process of ingesting such data into modeling software often involves multiple steps, requiring data restructuring to meet software-input requirements. The non-standardized reporting of water data makes data aggregation and reformatting a time-consuming process. Additionally, essential attributes necessary for modeling water treatment and mineral scale formation are frequently missing. Moreover, data gaps vary depending on the region of interest. Consequently, there is a pressing need for high-quality energy-water composition data that can be easily imported into water chemistry modeling software. To address this need, the National Energy Technology Laboratory has created the National Energy Water Treatment and Speciation (NEWTS) Database and Dashboard—a free online tool catering to community leaders and water researchers. NEWTS facilitates a comprehensive understanding of the composition of energy-related wastewater streams in the United States. The datasets provide detailed concentrations and speciation of major and minor aqueous compounds in energy-related wastewater streams, including power plant leachate, acid mine drainage, brackish water, and oil and gas produced water across the United States. Many of the aqueous species are critical minerals (Li, REEs) in high demand to modernize the world’s energy infrastructure. Many of the datasets also contain volumetric flow-rates needed to model the treatment and reuse scenarios in advanced aqueous chemistry software programs. The NEWTS Database and Dashboard offer public access to hitherto challenging-to-access datasets, presented in a standardized format that is tailored for easy input into aqueous chemistry modeling software. By performing the work needed to transform dispersed, disparate data sources into unified, model-ready datasets, NEWTS serves as an essential resource in advancing water treatment research and sustainable water resource management.

produced water management↗

Nuclear Fuels and Reprocessing Technologies: A U.S. Perspective

Reprocessing and/or waste management issues are of concern to the “back end” of the nuclear fuel cycle. Of course, there are a great many “nuclear fuel cycle” scenarios to consider; if not in practice, then at least in theory. The simplest conceptually is the “once through” fuel cycle in which the spent fuel is discarded. The more complex fuel cycle scenarios involve reprocessing spent nuclear fuels and a family of nuclear reactor technologies to accommodate burning and breeding for various military and commercial needs. Therefore, the selection of a specific “fuel cycle” is what ultimately imposes the engineering requirements of the reprocessing and waste management technologies. No one part is independent of the other parts in a fuel cycle flowsheet; all parts are fully integrated. This paper presents a summary of radiochemical processes, nuclear reactor technologies, nuclear fuel types, and the reprocessing technologies that serve the different nuclear fuel types. Comprehending how this series of topics are related to each other is a prerequisite to understanding the requirements of any reprocessing strategy. The summary materials presented here are selective, as opposed to comprehensive. More detailed information on any one subject can be found in the reference materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Direct Extraction of Lanthanide Oxides and Nitrates in Tributyl Phosphate

This work investigated the dissolution rate of lanthanide oxides and nitrates in a 30 vol % TBP-n-paraffin solvent (pre-equilibrated with various nitric acid concentrations) using visible (Vis) spectroscopy over time. Some dissolution mechanics were observed, such as an aqueous layer forming, considerably longer dissolution times for the heavier lanthanides (hours) vs. the lighter lanthanides (minutes), and the impacts of mixing lanthanide oxides or nitrates during dissolution. Neodymium, samarium, holmium, and erbium were selected due to their unique spectroscopic signatures and to represent the lighter (neodymium and samarium) and heavier (holmium and erbium) lanthanides. Even though europium does not have a strong absorbance in the range studied, europium was used in some instances to also represent the lighter lanthanides. Cerium oxide was used to representant dissolution of tetravalent lanthanides.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterization of Nitrate, Nitrite, Ammonia, and Tritium in D0220 Cores

This report describes characterization of nitrogen species (nitrate, nitrite, ammonia) in aqueous and solid phases in cores taken in borehole D0220 (well 299-E25-245) under crib 216-A-37-1 at the Hanford Site in 2022 to evaluate (a) the types of nitrogen species currently in the vadose zone and (b) the migration of nitrogen species in the vadose zone. Ammonia and tritium from PUREX decladding condensate were sporadically discharged to the crib from 1977 to 1989. During discharge operations, the estimated travel time through the vadose zone to groundwater was 2.5 to 9 months. By 2003, a characterization borehole (C4106) showed residual pore water with elevated tritium and nitrate in the first 100 ft of the vadose zone, which is likely from the crib. However, there was significantly more nitrate present at the shallowest depth (15 to 22 ft), which may indicate a different source for nitrate, such as adsorbed ammonia slowly being oxidized or nitrogen species precipitates slowly dissolving. In this study, more extensive nitrogen species characterization was done on D0220 cores (drilled in 2022) at 40- and 262-ft depths, which included (a) aqueous nitrate, nitrite, and tritium; (b) adsorbed ammonia; (c) nitrogen in carbonates (or other minerals dissolved in acidic acid); (d) nitrogen in iron oxides (or other minerals dissolved in oxalic acid); and (e) nitrogen in hard-to-extract minerals (minerals dissolved in nitric acid). High pore water nitrate (226 to 331 mg/L) at 40-ft depth measured in D0220 (2022) compared to 60 mg/L at 40-ft depth in C4106 (2003) may indicate nitrate is migrating deeper. Tritium concentrations (pore water 132,000 to 148,000 pCi/L) measured in D0220 at 40-ft depth in 2022 were considerably higher than in C4106 at 40-ft depth (160 pCi/L). Additional nitrogen species mass was present in adsorbed and precipitated phases in D0220 cores. Low adsorbed ammonia was measured at 40.1- and 261.7-ft depths. Low concentrations of carbonate associated nitrogen and iron oxide-associated nitrogen were present at 40.1 and 40.6 ft depths. Nitrogen species in solid phase extractions indicate nitrogen precipitates or aqueous nitrate or ammonia trapped in sediment microfractures that are coated by precipitates. Overall, the nitrogen species and tritium characterization at two depths in D0220 showed that additional nitrogen species were present in the vadose zone. In addition, elevated pore water nitrate in D0220 at 40 ft depth from 2022 may indicate vertical migration compared to C4106 nitrate profile from 2003. Analysis of additional depths in D0220 and spatial variability of the nitrate plume along the length of the crib (from surface electrical resistivity) would be extremely useful for this comparison.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Reactive transport modeling for supporting climate resilience at groundwater contamination sites

Abstract. Climate resilience is an emerging issue at contaminated sites and hazardous waste sites, since projected climate shifts (e.g., increased/decreased precipitation) and extreme events (e.g., flooding, drought) could affect ongoing remediation or closure strategies. In this study, we develop a reactive transport model (Amanzi) for radionuclides (uranium, tritium, and others) and evaluate how different scenarios under climate change will influence the contaminant plume conditions and groundwater well concentrations. We demonstrate our approach using a two-dimensional (2D) reactive transport model for the Savannah River Site F-Area, including mineral reaction and sorption processes. Different recharge scenarios are considered by perturbing the infiltration rate from the base case as well as considering cap-failure and climate projection scenarios. We also evaluate the uranium and nitrate concentration ratios between scenarios and the base case to isolate the sorption effects with changing recharge rates. The modeling results indicate that the competing effects of dilution and remobilization significantly influence pH, thus changing the sorption of uranium. At the maximum concentration on the breakthrough curve, higher aqueous uranium concentration implies that sorption is reduced with lower pH due to remobilization. To better evaluate the climate change impacts in the future, we develop the workflow to include the downscaled CMIP5 (Coupled Model Intercomparison Project) climate projection data in the reactive transport model and evaluate how residual contamination evolves through 2100 under four climate Representative Concentration Pathway (RCP) scenarios. The integration of climate modeling data and hydrogeochemistry models enables us to quantify the climate change impacts, assess which impacts need to be planned for, and therefore assist climate resiliency efforts and help guide site management.

54 ENVIRONMENTAL SCIENCES↗

Exploring Approaches for Accelerated Mass Spectrometric Detection of Fluorochemicals from Aqueous Solutions Using Indirect, Adsorbent-Facilitated Desorption Ionization

There is a growing need for rapid, low-cost analytical tools to screen water supplies for persistent contaminants. Due to their ubiquitous presence in the environment and their detrimental effects on human health, there is a public interest in widespread testing for perfluoroalkyl substances (PFAS). However, the most common methods for PFAS analysis can be time-intensive, requiring a preconcentration step followed by liquid chromatography–mass spectrometry (LC–MS), and are cost-prohibitive for most members of the public. To address these challenges, this study explores a novel method for rapid analysis of aqueous analytes by concentrating analytes on solid adsorbents and detecting them using mass spectrometric analysis via desorption ionization directly from the adsorbent surface. We demonstrate this general approach of indirect solution analysis (ISA) with desorption electrospray ionization (ISA-DESI) and laser desorption ionization (ISA-LDI). Various adsorbent materials were screened, including commercial mesoporous carbons, alumina, and metal–organic frameworks (MOFs). Using ISA-DESI, we consistently detect concentrations as low as 5–100 parts per trillion (ppt) for perfluorooctanoic acid (PFOA) and 10–100 ppt for perfluoroundecanoic acid (PFUnDA). This approach enables rapid detection in under 5 min, making it suitable for applications requiring trace detection with fast response times. We further demonstrate the use of ISA-DESI on a range of environmentally relevant contaminants. Advantages of this indirect solution analysis approach include simplified sample preparation, accelerated analysis, and low cost with readily available materials, making it a promising tool to accelerate mass spectrometric PFAS detection for identifying contaminated sites, performing laboratory studies, and monitoring industrial waste streams.

Bays, Nathan Robert [Sandia National Laboratories ↗

Iodine Co-Precipitation with Calcium Carbonate in the Presence of Silica Ions - 20360

Historical releases of I-129 to the subsurface at the U.S. Department of Energy Hanford Site have resulted in large dilute plumes that cover an area of over 50 km{sup 2}. The most concentrated I-129 plume is associated with the 200 West Area in the 200-UP-1 operable unit of the Hanford Central Plateau, where peak concentrations have been measured up to 30 times the drinking water standard of 1 pCi/L. The mobility of iodine depends on many factors, including chemical speciation, pH, redox conditions, as well as the presence of organic matter, calcium carbonate minerals and microbial activities. Speciation measurements estimate that the majority of the iodine (∼76%) in Hanford groundwater exists as iodate. Information on processes that affect iodate mobility in the Hanford subsurface support evaluation of environmental management options for the I-129 plumes. Iodate can be incorporated into calcium carbonate, which is a potential mechanism of naturally attenuating radioiodine in groundwater. However, the silica content in porewater may impact the contaminant-calcium carbonate incorporation process. Silica is one of the most abundant elements in nature and can have an impact on chemical weathering of alkaline-earth carbonates in the environment. Hence, this research aims to advances knowledge of the iodine co-precipitation process with calcium carbonate in the presence of silica. This information supports the technical basis evaluation of natural attenuation for I-129. Samples for these studies were prepared using calcium carbonate-forming solutions that included certified grade sodium meta-silicate nonahydrate (Na{sub 2}SiO{sub 3}), calcium chloride dehydrate (CaCl{sub 2}.2H{sub 2}O), sodium carbonate (NaCO{sub 2}), and sodium hydroxide (NaOH) solutions for pH adjustments. Triplicate samples were prepared with silica concentrations in the solution of 0 mM, 0.5 mM and 20 mM, mixed with an iodate standard (1000 ppm of IO{sub 3}{sup -} in H{sub 2}O) and sampled over a one-week period. Preliminary data analyses suggest that less iodine remains in solution in the presence of silica (average remaining aqueous fraction 0.23±0.03 at 20 mM of Si) relative to samples without silica (0.52±0.06); an indication that more iodine has been sorbed or incorporated into precipitates. However, the mechanisms for this behavior are still under investigation and need to be interpreted relative to pore water compositions that are representative of Hanford site-specific conditions. Scanning electron microscope equipped with energy dispersive spectroscopy (SEM-EDS) analyses were performed to observe the solid phase morphology in these experiments and showed rhombohedral calcite crystals covered with amorphous Si floccules. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗