Metal-Encapsulated, Polymer-Containing Halide Salt Composites as Potential Long-Term Hosts for Radioiodine: Evaluating Halmets, Polyhalmets, and Halcermets.

This paper presents composite waste form concepts for radioiodine immobilization including halide-metal (halmet) composites, polymer-halide-metal (polyhalmet) composites, and halide-ceramic-metal (halcermet) composites with data from experiments to evaluate these ideas. The encapsulant metal of choice for the pellets was Bi0, and a cold-press-and-sinter approach was used for creating the pellets. A polymer (i.e., polyacrylonitrile or PAN) phase was included in some composite forms because this porous, passive polymer is used as a host matrix for active chemisorption-based getters. Metals of Ag0, Bi0, and Cu0 were separately embedded into PAN beads, which were loaded with iodine in static tests. Included are details of experiments where PAN removal from the iodine-loaded composite beads was evaluated to reduce the overall volume of the final waste requiring immobilization and to improve the thermal stability of the final composite form. While these experiments demonstrate new concepts for radioiodine immobilization, more work is needed to fully understand the limitations of these approaches and further optimizations are needed before implementation at larger scales is feasible.

Expired blood transfusion and mortality outcomes in combat trauma patients.

BACKGROUND: Expired blood can be transfused if clinically indicated but outcome data do not exist. We hypothesized that modestly outdated blood can effectively support a hemorrhaging patient until surgical control is achieved. This study assessed whether expired blood was associated with mortality in combat trauma patients. STUDY DESIGN AND METHODS: A retrospective analysis of Armed Services Blood Program and Department of Defense Trauma Registry databases evaluated combat casualty records (2001-2023). The intervention of interest was transfusion of at least one unit of whole blood (WB), red blood cells (RBC), or platelets within one week past expiration. The outcome of interest was mortality at discharge. A control cohort that only received in-date blood was matched to the treatment cohort for logistic regression analysis. RESULTS: One hundred patients received expired RBCs (86), WB (11), and platelets (3). Mortality at discharge was 11.6% for expired RBC recipients and 13.4% for the control cohort (p = .97). After adjustment for injury severity, expired RBCs were not associated with mortality (OR = 0.40 [95% CI, 0.14-1.16]; p = .09). Of 10 patients who received the most expired RBCs by volume or storage duration, two were deceased at discharge. All 14 expired WB and platelet recipients were alive at discharge, but sample sizes were underpowered for regression analysis. DISCUSSION: Transfusion of modestly outdated RBCs was not associated with mortality in combat trauma patients. Expired WB and platelet recipients did well, but sample sizes were too small to draw significant conclusions. Expired blood should be further investigated for possible use in extenuating circumstances.

Synthesis and properties of anhydrous rare-earth phosphates, monazite and xenotime: a review.

The synthesis methods, crystal structures, and properties of anhydrous monazite and xenotime (REPO4) crystalline materials are summarized within this review. For both monazite and xenotime, currently available Inorganic Crystal Structure Database data were used to study the effects of incorporating different RE cations on the unit cell parameters, cell volumes, densities, and bond lengths. Domains of monazite-type and xenotime-type structures and other AXO4 compounds (A = RE; X = P, As, V) are discussed with respect to cation sizes. Reported chemical and radiation durabilities are summarized. Different synthesis conditions and chemicals used for single crystals and polycrystalline powders, as well as first-principles calculations of the structures and thermophysical properties of these minerals are also provided.

Phosphate-Based Dechlorination of Electrorefiner Salt Waste using a Phosphoric Acid Precursor.

Electrochemical processing of spent nuclear fuel in molten chloride salts results in radioactive salt waste. Chlorine removal from the salt has been identified as an effective and efficient first step in the management of high-level waste. In this work, a simple salt was dechlorinated with a phosphoric acid phosphate precursor, resulting in a glassy dechlorinated product. The dechlorination efficacy was evaluated in air and argon environments. This work serves as an initial step to advance the Technological Readiness Level of H3PO4-based dechlorination step toward implementation of iron phosphate waste forms to immobilize electrochemical fuel reprocessing salt waste streams.

FAIR Island: real-world examples of place-based open science.

The relationship between people, place, and data presents challenges and opportunities for science and society. While there has been general enthusiasm for and work toward Findable, Accessible, Interoperable, and Reusable (FAIR) data for open science, only more recently have these data-centric principles been extended into dimensions important to people and place-notably, the CARE Principles for Indigenous Data Governance, which affect collective benefit, authority to control, responsibility, and ethics. The FAIR Island project seeks to translate these ideals into practice, leveraging the institutional infrastructure provided by scientific field stations. Starting with field stations in French Polynesia as key use cases that are exceptionally well connected to international research networks, FAIR Island builds interoperability between different components of critical research infrastructure, helping connect these to societal benefit areas. The goal is not only to increase reuse of scientific data and the awareness of work happening at the field stations but more generally to accelerate place-based research for sustainable development. FAIR Island works reflexively, aiming to scale horizontally through networks of field stations and to serve as a model for other sites of intensive long-term scientific study.

Effects of NO2 aging on bismuth nanoparticles and bismuth-loaded silica xerogels for iodine capture.

The capture of long-lived radioactive iodine (129I) from oxidizing off-gasses produced from reprocessing used nuclear fuel is paramount to human health and environmental safety. Bismuth has been investigated as a viable iodine getter but the phase stability of bismuth-based sorbents in an oxidizing environment have not yet been researched. In the current work, bismuth nanoparticle-based sorbents, as free particles (Bi-NPs) and embedded within silica xerogel monoliths made with a porogen (TEO-5), were exposed to I2(g) before and after aging in 1 v/v% NO2 at 150 °C. For unaged sorbents, BiI3 was the dominant phase after iodine capture with 8-30 mass% BiOI present due to native Bi2O3 on the surface of the unaged nanoparticles. After 3 h of aging, 82 mass% of the Bi-NPs was converted to Bi2O3 with only a small amount of iodine captured as BiOI (18 mass%). After aging TEO-5 for 3 h, iodine was captured as both BiI3 (26 %) and BiOI (74 %) and no Bi2O3 was detected.". Additionally, bismuth lining the micrometer-scale pores in the TEO-5 led to enhanced iodine capture. In a subsequent exposure of the sorbents to NO2 (secondary aging), all BiI3 converted to BiOI. Thus, direct capture of iodine as BiOI is desired (over BiI3) to minimize loss of iodine after capture.

Dehalogenation reactions between halide salts and phosphate compounds.

Reactions between phosphoric acid [H3PO4] or ammonium hydrogen phosphates [i.e., NH4H2PO4, (NH4)2HPO4] and halide salts can be used to dehalogenate (remove halides from) salt-based waste streams, where the process of removing halides yields products that have more efficient disposal pathways for repository storage. In this context, the term efficiency is defined as higher waste loadings and simplified immobilization processes with potential for recycle of certain salt components (e.g., 37Cl as H37Cl or NH4 37Cl). The main streams identified for these processes are nuclear wastes generated during electrochemical reprocessing of used nuclear fuel as well as used halide salts from molten salt reactor operation. The potential byproducts of these reactions are fairly consistent across the range of halide species (i.e., F, Cl, Br, I) where the most common are hydrogen halides [e.g., HCl(g)] or ammonium halides (e.g., NH4Cl). However, trihalide compounds (e.g., NCl3), nitrogen triiodide ammine adducts [NI3·(NH3) x ], and ammonium triiodide (NH4I3) are also possible. Several of these byproducts (i.e., NCl3, NBr3, NI3, and NH4I3) are shock-sensitive contact explosives so their production in these processes must be tracked and carefully controlled, which includes methods of immediate neutralization upon production such as direct transport to a caustic scrubber for dissolution. Several benefits arise from utilizing H3PO4 as the phosphate additive during dehalogenation reactions for making iron phosphate waste forms including more oxidized iron (higher Fe3+:Fe2+ ratios), higher chemical durabilities, and the avoidance of trihalides, but the byproducts are hydrogen halides, which are corrosive and require special handling.

Radioiodine sorbent selection criteria.

Methods for preventing radioiodine from entering the environment are needed in processes related to nuclear energy and medical isotope production. The development and performance of many different types of sorbents to capture iodine have been reported on for decades; however, there is yet to be a concise overview on the important parameters that should be considered when selecting a material for chemically capturing radioiodine. This paper summarizes several criteria that should be considered when selecting candidate sorbents for implementation into real-world systems. The list of selection criteria discussed are 1) optimal capture performance, 2) kinetics of adsorption, 3) performance under relevant process conditions, 4) properties of the substrate that supports the getter, and 5) environmental stability and disposition pathways for iodine-loaded materials.

Bilateral Pneumothoraces in a Tandem Parachuting Passenger Without Traumatic Impact: A Case Report.

In parachuting, orthopedic and head injuries are well-documented risks associated with the parachute deployment and landing phases. Thoracic injuries have only been seen on rare occasion in conjunction with direct impact trauma. In this report, we detail a case of a young, healthy, tandem skydiving passenger who suffered bilateral pneumothoraces with delayed symptom onset, with no identifiable injury during the jump or landing. Exploring the forces of the parachute "opening shock," we suggest a plausible compressive mechanism for this novel presentation, as well as briefly discuss the options for diagnosis and conservative management of pneumothorax in the operational context. While this is an exceedingly rare event, pneumothorax should be considered in patients complaining of thoracic symptoms following a skydive.

Role of Zeolite Structural Properties toward Iodine Capture: A Head-to-head Evaluation of Framework Type and Chemical Composition.

This study evaluated zeolite-based sorbents for iodine gas [I2(g)] capture. Based on the framework structures and porosities, five zeolites, including two faujasite (FAU), one ZSM-5 (MFI), one mesoMFI, one ZSM-22 (TON), as well as two mesoporous materials, were evaluated for I2(g) capture at room temperature and 150 °C in an iodine-saturated environment. From these preliminary studies, the three best-performing zeolites were ion-exchanged with Ag+ and evaluated for I2(g) capture under similar conditions. Energy-dispersive X-ray spectroscopy data suggest that Ag-FAU frameworks were the materials with the highest capacity for I2(g) in this study, showing ∼3× higher adsorption compared to Ag-mordenite (Ag-MOR) at room temperature, but X-ray diffraction measurements show that the faujasite structure collapsed during the adsorption studies because of dealumination. The Ag-MFI zeolites are decent sorbents in real-life applications, showing both good sorption capacities and higher stability. In-depth analyses and characterizations, including synchrotron X-ray absorption spectroscopy, revealed the influence of structural and chemical properties of zeolites on the performance for iodine adsorption from the gas phase.

Review of recent developments in iodine wasteform production.

Radioiodine capture and immobilization is not only important to consider during the operation of reactors (i.e., I-131), during nuclear accidents (i.e., I-131 and I-129) or nuclear fuel reprocessing (i.e., I-131 and I-129), but also during disposal of nuclear wastes (i.e., I-129). Most disposal plans for I-129-containing waste forms (including spent nuclear fuel) propose to store them in underground repositories. Here, iodine can be highly mobile and, given its radiotoxicity, needs to be carefully managed to minimize long-term environmental impacts arising from disposal. Typically, any process that has been used to capture iodine from reprocessing or in a reactor is not suitable for direct disposal, rather conversion into a wasteform for disposal is required. The objectives of these materials are to use either chemical immobilization or physical encapsulation to reduce the leaching of iodine by groundwaters. Some of the more recent ideas have been to design capture materials that better align with disposal concepts, making the industrial processing requirements easier. Research on iodine capture materials and wasteforms has been extensive. This review will act as both an update on the state of the research since the last time it was comprehensively summarized, and an evaluation of the industrial techniques required to create the proposed iodine wasteforms in terms of resulting material chemistry and applicability.

Metallic technetium sequestration in nickel core/shell microstructure during Fe(OH)2 transformation with Ni doping.

This study investigates the impacts of Ni doping on technetium-99 (Tc) sequestration in aqueous solutions through transformation of Fe(OH)2(s) to iron spinel (magnetite) under alkaline conditions. Extensive solid characterization was performed for the mineral phases produced, as well as the Tc/Ni speciation and distribution within these phases. X-ray diffraction results show that iron spinel was the dominant mineral product without detectable Ni incorporation. The doped Ni ions mainly precipitated as fine Fe/Ni oxide/hydroxide particles, including strongly reduced nanometer-sized spheroidal Ni-rich and metallic Ni phases. High-resolution analytical scanning transmission electron microscopy using energy dispersive X-ray spectroscopy and electron energy loss spectroscopy on the produced solid samples (focused ion beam-prepared specimens) revealed three Tc distribution domains dominated by nanocrystals and, especially, a Tc-rich metallic phase. Instances of metallic Tc were specifically found in spheroidal, Ni-rich and metallic nanoparticles exhibiting a core/shell microstructure that suggests strong reduction and sequential precipitation of Ni-Tc-Ni. Mass balance analysis showed nearly 100% Tc removal from the 4.8 × 10-4 M Tc solutions. The finding of the metallic Tc encapsulation indicates that Tc sequestration through Ni-doped Fe(OH)2(s)-to-iron spinel transformation process likely provides an alternative treatment pathway for Tc removal and could be combined into further waste treatment approaches.

Dechlorination Apparatus for Treating Chloride Salt Wastes: System Evaluation and Scale-Up.

This paper describes an apparatus used to remove chlorine from chloride salt-based nuclear wastes from electrochemical reprocessing and/or chloride-based molten salt reactors (MSRs) through dechlorination by reacting the salts with ammonium dihydrogen phosphate (NH4H2PO4 or ADP) at temperatures up to 600 °C to produce NH4Cl as a byproduct. The benefits of removing the Cl from these salts include 37Cl recovery from Cl-based MSR salts, formation of UCl3 from the NH4Cl, as well as removal of Cl from the salts and conversion of the salt cations to oxides to allow for immobilization in a chemically durable iron phosphate waste form. This generation-2 system is an improvement over the generation-1 system and provides a means for scaling up salt throughput as well as NH4Cl recovery. The generation-2 system includes a five-zone furnace so the temperature of the four-zone gradient furnace can be tailored to control the location of NH4Cl condensation on a four-piece fused quartz off-gas system. Both ADP and NH4Cl decomposition reactions include the production of NH3 and acids (i.e., H3PO4 and HCl, respectively), so careful temperature control is needed during the ADP-salt reactions to maximize the NH4Cl production and minimize NH4Cl decomposition. In two sets of experiments run in the generation-1 and generation-2 apparatuses, NH4Cl yields were ≥5.5-fold higher for the new system compared to the original prototype system and the batch sizes can be ≥2.5-fold higher. In addition, some thermodynamic experiments evaluating the reactions of ADP + KCl as well as decomposition of pure NH4Cl were performed to assess the temperatures of the reactions and identify off-gas products.

Energy-dispersive X-ray spectroscopy and atom-probe tomography data quantifying component-ratios of multicomponent nano-precipitates in ion-irradiated ceria.

Samples of ∼1 µm films of CeO2 doped with 2 wt% Mo, 1.5 wt% Ru, 0.75 wt% Pd, 0.5 wt% Re and 0.25 wt% Rh grown with pulsed laser deposition were irradiated with I2+ ions (610 °C and 730 °C, 1016 and 5 × 1016 I2+/cm2). For selected samples post-irradiation heat treatment was conducted (900 °C, 1100 °C). The specimens were sectioned with focused ion beam milling and characterized in a transmission electron microscope with energy-dispersive x-ray spectroscopy, and with atom-probe tomography. Energy-dispersive x-ray spectroscopy was used to obtain elemental maps showing the distribution of dopants in the specimen after exposure. Some of these maps are discussed in detail in our companion article "Formation of multicomponent alloy particles in doped ceria under I2+ ion irradiation and thermal annealing" in the Journal of Nuclear Materials [1]. Advanced computational analysis could be used to more accurately quantify local compositions. Data is provided for additional regions of interest and one additional irradiation condition. The doped ceria film that was heat treated at 1100 °C delaminated from the substrate in most places. Samples were extracted from the underside of a delaminated piece and analyzed with atom-probe tomography. The resulting data show ceria and a Mo-rich particle and demonstrate that this approach is feasable in principle to study local compositions in a sample exposed to such extreme conditions.

Disparity in Medicare payments by gender and training track in female pelvic medicine and reconstructive surgery.

BACKGROUND: Gender disparities in medicine have been demonstrated in the past, including differences in the attainment of roles in administration and in physician income. OBJECTIVE: Our objective was to determine the differences in Medicare payments based on the provider gender and training track among female pelvic medicine and reconstructive surgeons. STUDY DESIGN: Medicare payments from the Provider Utilization Aggregate Files were used to determine the payments made by Medicare to urogynecologists. This database was merged with the National Provider Identifier registry with information on subspecialty training, years since graduation, and the geographic pricing cost index used for Medicare payment adjustments. Physicians with <90% female patients and those who graduated medical school <7 years ago in obstetrics and gynecology or <8 years ago in urology were excluded. The effects of gender, specialty of training, number of services provided, years of practice, and geographic pricing cost index on physician reimbursement were evaluated using linear mixed modeling. RESULTS: A total of 578 surgeons with female pelvic medicine and reconstructive surgery subspecialty training met the inclusion criteria. Of those, 517 (89%) were trained as gynecologists, whereas 61 (11%) were trained as urologists. Furthermore, 265 (51%) of the gynecology-trained surgeons and 39 (80%) of the urology-trained surgeons were women. Among the urology-trained surgeons, the median female surgeon was paid $85,962 and their male counterparts were paid $121,531 (41% payment difference). In addition, urology-trained female pelvic medicine and reconstructive surgery surgeons performed a median of 1135 services and their male counterparts performed a median of 1793 services (57% volume difference). Similarly, among gynecology-trained surgeons, the median female payment was $59,277 with 880 services performed, whereas male gynecology-trained surgeons received a median of $66,880 with 791 services performed, representing a difference of 12% in payments and 11% in services. With linear mixed modeling, male physicians were paid more than female physicians while controlling for specialty training, number of services performed, years of practice, and geographic pricing cost index (P<.001). CONCLUSION: Although Medicare payments are based on an equation, differences in reimbursement by physician gender exist in female pelvic medicine and reconstructive surgery with female surgeons receiving lower payments from Medicare. The differences in reimbursement could not be solely explained by differences in patient volume, area of practice, or years of experience alone, suggesting that, similar to other fields in medicine, female surgeons in female pelvic medicine and reconstructive surgery are not paid as much as their male counterparts.

Iodine Capture with Mechanically Robust Heat-Treated Ag-Al-Si-O Xerogel Sorbents.

Various radionuclides are released as gases during reprocessing of used nuclear fuel or during nuclear accidents including iodine-129 (129I) and iodine-131 (131I). These isotopes are of particular concern to the environment and human health as they are environmentally mobile and can cause thyroid cancer. In this work, silver-loaded heat-treated aluminosilicate xerogels (Ag-HTX) were evaluated as sorbents for iodine [I2(g)] capture. After synthesis of the base NaAlSiO4 xerogel, a heat-treatment step was performed to help increase the mechanical integrity of the NaAlSiO4 gels (Na-HTX) prior to Ag-exchanging to create Ag-HTX xerogels. Samples were characterized by powder X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, Brunauer-Emmett-Teller analysis, gravimetric iodine loading, nanoindentation, and dynamic mechanical analysis. The structural and chemical analyses of Ag-HTX showed uniform distribution of Ag throughout the gel network after Ag-exchange. After I2(g) capture, the AgI crystallites were observed in the sorbent, verifying chemisorption as the primary iodine capture mechanism. Iodine loading of this xerogel was 0.43 g g-1 at 150 °C over 1 day and 0.52 g g-1 at 22 °C over 33 days. The specific surface area of Ag-HTX was 202 m2 g-1 and decreased to 87 m2 g-1 after iodine loading. The hardness of the Na-HTX was >145 times higher than that of the heat-treated aerogel of the same starting composition. The heat-treatment process increased Young's modulus (compressive) value to 40.8 MPa from 7.0 MPa of as-made xerogel, demonstrating the need for this added step in the sample preparation process. These results show that Ag-HTX is a promising sorbent for I2(g) capture with good iodine loading capacity and mechanical stability.

Perovskite-Derived Cs2SnCl6-Silica Composites as Advanced Waste Forms for Chloride Salt Wastes.

Advanced materials and processes are required to separate halides and fission products from complex salt waste streams associated with the chemical reprocessing of used nuclear fuels and molten salt reactor technologies for immobilization into chemically durable waste forms. In this work, we explore an innovative concept using metal halide perovskites as advanced host phases to incorporate Cs and Cl with very high waste loadings. Wet chemistry-synthesized Cs2SnCl6 powders from CsCl salt solutions are successfully encapsulated into a silica matrix to form a composite using low-temperature spark plasma sintering with tunable Cs and Cl loadings up to 31 and 26 wt %, respectively. Chemical durability testing of the composite waste forms by semi-dynamic leaching experiments demonstrates that an incongruent leaching mechanism dominates the release of Cs and Cl. The metal halide perovskite-silica composite waste forms display exceptional chemical durability with the long-term release rates of Cs and Cl comparable to or outperforming the state-of-the-art waste form materials but with significantly higher waste loadings. The scalable synthesis of the metal halide perovskite from wet chemistry processes opens up new opportunities in designing advanced waste forms for salt wastes with very high waste loadings and exceptional chemical durability for the sustainable development of advanced fuel cycles and next-generation reactor technologies.