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At least 433 records · Page 24

Benchmarking Concentration and Extraction Methods for Wastewater-Based Surveillance of Eight Human Respiratory Viruses: Implications for Rapid Application to Novel Pathogens

To provide early warning and support a rapid response to a novel virus through wastewater surveillance, it would be ideal to understand in advance which concentration and extraction methods are likely to be effective for dPCR-based methods, depending on virus characteristics. In this study, we spiked raw wastewater samples with eight human respiratory viruses and processed them with four methods that concentrate and/or extract nucleic acids from both liquid and solid fractions (Promega, Nanotrap, and InnovaPrep) or only the solid fraction of wastewater (Solids). Our findings provide encouraging evidence that all four methods combined with dPCR could detect an emerging virus in wastewater, although they differed in sensitivity. The pattern of recovery efficiency for adenoviruses, coronaviruses, and influenza A viruses was consistent across methods, with Promega producing higher median recovery efficiencies, while distinct patterns were observed for coxsackieviruses. We also normalized the concentration data with two endogenous fecal indicators, PMMoV and Carjivirus (formerly crAssphage). We found that normalization could reduce method-associated differences if the indicator exhibited a recovery pattern similar to that of the target virus. These findings can guide the selection of concentration and extraction methods for wastewater monitoring based on the properties of target viruses, thus enhancing pandemic preparedness.

Biological and medical sciences↗

Solvent-driven aqueous separations for hypersaline brine concentration and resource recovery

Solvent-driven separation processes can extract water and high-value minerals from high salinity or contaminated brines, simultaneously reducing the environmental impact of brine disposal and enabling resource recovery. The efficient dewatering of hypersaline brines is essential for the sustainable minimal and zero liquid discharge processing of industrial wastewaters. Fractional crystallization can selectively extract ions from contaminated waste streams, allowing critical materials to be recycled, including transition and lanthanide metals required for renewable energy generation and storage. Mass transfer in solvent-driven water extraction occurs across a liquid–liquid interface, eliminating the scaling and fouling of membrane and heat exchanger surfaces and limiting the need for extensive pretreatment. Solvent-driven fractional crystallization can leverage sequential treatment and control of process conditions to rapidly recover salts without requiring evaporation of water. Despite promising applications, the principles and potential of solvent-driven aqueous separations remain poorly understood. This critical review explores the opportunities presented by solvent-based aqueous separations from the molecular to process scale, evaluating the chemistry of solvation and system design in the broader context of desalination, resource recovery, water softening, and mineral production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of fragment formation on shear viscosity in the nuclear liquid-gas phase transition region

Within the improved quantum molecular dynamics (ImQMD) model we follow the evolution of nuclear matter for planar Couette flow in a periodic box. We focus on the region of liquid-gas phase transition and extract the shear viscosity coefficient from the local stress tensor, directly following the viscosity definition. Here, by switching on and off the mean field and thus inducing the phase transition, we are able to observe the impact of clumping in the phase transition region on the viscosity.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

The radiation chemistry of ionic liquids: A review

Ionic liquids have received increasing attention as media for radiochemical separations. Recent literature includes examinations of the efficiencies and mechanisms of the solvent extraction of lanthanides, actinides and fission products into ionic liquid solutions. For radiochemical applications, including as replacement solvents for nuclear fuel reprocessing, a thorough understanding of the radiation chemistry of ionic liquids will be required. Such an understanding can be achieved based on a combination of steady-state radiolysis experiments coupled with post-irradiation product identification and pulse-radiolysis experiments to acquire kinetic information. These techniques allow for the elucidation of radiolytic mechanisms. This contribution reviews the current ionic liquid radiation chemistry literature as it affects separations, with these considerations in mind.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Transformers for Lunar Extreme Environments: Ensuring Long-Term Operations in Regions of Darkness and Low Temperatures: II - Phase

This report shows how solar power could enable robotic operations in permanently shaded regions at lunar poles, to extract water ice and further produce liquid hydrogen and oxygen (LH2/LO2) propellant. The power needs are derived from an Architecture for Human Exploration of Mars based entirely on lunar propellant. The extraction of 10 metric tons of water per day (at 10% water in regolith) requires approx. 0.6 MW thermal power. Additional approx. 2 MW electric power are required to produce 7.5 metric tons of LH2/LO2 propellant per day, as needed by the architecture. To provide power to processing equipment inside Shackleton Crater, optimal locations are determined on the crater rim, from which several reflecting TransFormers (TFs) would redirect sunlight, achieving a combined period of illumination of approx. 99% of the year. A single 40-m diameter reflector could provide up to 1 MW solar power. Inflatable rigidizable tower support structures raise reflectors above ground for better solar exposure. There are trade-offs: e.g., two reflectors at ground level would provide the same combined total illumination as a single tower approx. 100-m tall. Such a TF based on a 100-m tower made with inflatable 2-m beams and 40-m diameter reflectors would be of similar dimensions as an MSL-class rover (approx. 1000 kg, 10 m(exp 3)). A TF-prospector rover combo could be designed and deployed in a Discovery-class mission searching for water. The TransFormers would be nodes of a Lunar Utilities Infrastructure that provides solar power year-round in the proximity of the pole, as well as local data transmission andintermittent direct to earth communications. This infrastructure would be instrumental infacilitating the development of a lunar economy.

fuel↗

Liquid sample processor

Processor is automatic and includes series of extraction tubes packed with fibrous absorbent material of large surface area. When introduced into these tubes, liquid test samples become completely absorbed by packing material as thin film.

Jahnsen, V. J.↗

Extraction and Separation of Rare-Earth Elements from Coal Fly Ash and Leachate using a Recyclable Ionic Liquid

Coal fly ash (CFA) can be a promising source for recovering rare-earth elements (REEs), as it contains a broad range of REEs with average concentrations frequently exceeding those in traditional rare earth mines. Recent research from our group has demonstrated that REEs can be preferentially extracted from CFA solids using a recyclable ionic liquid (IL), betainium bis-(trifluoromethylsulfonyl)imide ([Hbet][Tf2N]). When CFA was heated with the mixture of IL and an aqueous solution above 65°C, most leached REEs partitioned into the IL phase and were separated from the bulk elements. Subsequent acid stripping of the REE-loaded IL removed the REEs and regenerated the IL for reuse in multiple extraction cycles. This IL-based REE-CFA recovery method has been applied to ten CFA samples derived from different coal sources, including ash recovered from disposal ponds. Analysis of 34 elements confirmed the process consistently achieved high REE recovery efficiency, with strong selectivity over bulk and trace elements across diverse CFA types. In addition to the IL-solid extraction, the performance of [Hbet][Tf2N] in extracting REEs from fly-ash leachates have been evaluated by four commonly used leaching reagents, including HCl, HNO3, H2SO4, and citrate. During the IL-leachate extraction, [Hbet][Tf2N] was mixed and heated with a Class C fly ash leachate generated from each leaching reagent, followed by an acid stripping. It was observed that the partitioning and recovery of REEs increased as the leachate pH increased from 3 to 11. Among the investigated leachates, HCl and citrate proved to be the most compatible with IL extraction, exhibiting a slightly higher REE recovery and a lower non-REE co-extraction compared to the IL-solid extraction. Sc, Y, Nd, Sm, Gd, Dy, and Yb consistently showed a high recovery rate from both CFA solids and leachates. Notably, Pr, Tb, and Ho, which were not previously leached from the CFA solids, were partially recovered from the leachates. Overall, our studies revealed the strong potential of [Hbet][Tf2N] for effectively recovering REEs from leachates, highlighting its applicability as a sustainable strategy for other aqueous REE feedstocks. Furthermore, a techno-economic analysis will be performed to quantify the economic viability of the IL-based REE recovery method and guide future process improvement.

42 ENGINEERING↗

Next generation solvent performance in the modular caustic side solvent extraction process - 15495

Changes to the Modular Caustic Side Solvent Extraction Unit (MCU) flow-sheet were implemented in the facility. Implementation included changing the scrub and strip chemicals and concentrations, modifying the O/A ratios for the strip, scrub, and extraction contactor banks, and blending the current BoBCalixC6 extractant based solvent in MCU with clean MaxCalix extractant based solvent. During the successful demonstration period, the MCU process was subject to rigorous oversight to ensure hydraulic stability and chemical/radionuclide analysis of the key process tanks (caustic wash tank, solvent hold tank, strip effluent hold tank, and decontaminated salt solution hold tank) to evaluate solvent carryover to downstream facilities and the effectiveness of cesium removal from the liquid salt waste. Results indicated the extraction of cesium was significantly more effective with an average Decontamination Factor (DF) of 1,129 (range was 107 to 1,824) and that stripping was effective. The contactor hydraulic performance was stable and satisfactory, as indicated by contactor vibration, contactor rotational speed, and flow stability; all of which remained at or near target values. Furthermore, the Solvent Hold Tank (SHT) level and specific gravity was as expected, indicating that solvent integrity and organic hydraulic stability were maintained. The coalescer performances were in the range of processing results under the BOBCalixC6 flow sheet, indicating negligible adverse impact of NGS deployment. After the Demonstration period, MCU began processing via routine operations. Results to date reiterate the enhanced cesium extraction and stripping capability of the Next Generation Solvent (NGS) flow sheet. This paper presents process performance results of the NGS Demonstration and continued operations of MCU utilizing the blended BobCalixC6-MaxCalix solvent under the NGS flowsheet. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Organic Matter in Itokawa Particles

The first Hayabusa mission returned samples from the near-Earth S-type asteroid 25143 Itokawa to Earth in 2010[1]. Although Itokawa has a lithology related to ordinary chondrites(OCs) that typically have low organic contents, several Itokawa particles were found to contain organic matter (OM)[2-5]. However, there was not an explicit conclusion to the origin of the observed OMin these early studies. We have extended our search for OM into other Itokawa grains. Here, we report extraterrestrial OM (macromolecular carbon and amino acids) observed in six Itokawa particles(including a category1 particle: RA-QD02-0162[#62; also nicknamed “Amazon”],and five category3 carbon-rich particles:RA-QD02-0012[#12], RA-QD02-0078[#78], RB-CV-0029[#29], RB-CV-0080 [#80] and RB-QD04-0052[#52]).All allocated Itokawa samples were initially analysed by spot and point-by-point mapping Raman spectroscopic analysis at the Open University, UK. Amazon was then transferred and mounted into indium on an aluminium stub, which was studied with a NanoSIMS 50L ion microprobe for its H,C,N isotopic compositions. The rest of the samples were mounted in sterile gold foils, and the amino acid contents of their acid hydrolysed hot water extracts were obtained with a liquid chromatography with tandem fluorescence and accurate mass detection at NASA Goddard Space Flight Center, USA. Based on the observation of the Raman parameters(e.g. the peak locations and widths of the defect (D) and graphite (G) bands)[6], a significant variety of carbonaceous materials has been observed in Amazon. The carbonaceous materials include primitive and unaltered OM that shares similarity with the IOM in primitive (CI,CM,CR) carbonaceous chondrites, as well as OM that has been heavily graphitised. The organic structure of the heated material is best represented by nanocrystalline graphite, comparable to that observed for metamorphosed meteorites (e.g., L3–6 Inman, Tieschitz and New Concord,CV3 Allende, and EH4 Indarch),suggesting peak metamorphic temperatures (PMT) of >~600°C. The thermal history recorded in the graphitic OM agrees with PMT estimates for returned Itokawa regolith grains (600–800°C)[7].We have obtained the H,C,N isotopic compositions for the primitive OM in Amazon, which exhibits unambiguously extraterrestrial isotopic signatures (δD = +4868±2288‰; δ13C = −24±5‰; δ15N = +344±20‰), contrasting to the typically negative isotopic values obtained for terrestrial organic matter[8]. The δD and δ13C values of the organic material in Amazon are comparable to OCs, however, the δ15N value is higher than that typically observed for OCs (δ15N = −47 to +36‰), and is similar to that of CRs (δ15N = +153 to +309‰)[9].Our data suggest a genetic link between the primitive organic material observed in Itokawa to CRs and IDPs for they share similar D, 13C and 15N enrichments[10].The high carbon contents of the five category 3 Itokawa particles suggest potentially higher OM abundances, hence we extracted and analysed amino acids in these samples. Although terrestrial contamination was observed primarily as L-protein amino acids, several terrestrially uncommon non-protein amino acids were also observed at low abundances, such as β-aminoisobutyric acid (β-AIB),β-amino-n-butyric acid (β-ABA), and β-alanine. Itokawa amino acid content observed here was dissimilar to thermally altered OCs, but preliminarily analogous to more aqueously altered CR2s.Continued evolution of Itokawa is evident by the in fall of primitive organic material derived from CRs/IDPs, accounting for a complex interplay between the remnant Itokawa silicates with exogenous organics. The results reported here are the first evidence of extraterrestrial OM in asteroid material from a sample-return mission, showcasing a working protocol for analysing samples returned by the Hayabusa2 and OSIRIS-REx missions

Q. H. S. Chan↗

Supported liquid inorganic membranes for nuclear waste separation

A system and method for the extraction of americium from radioactive waste solutions. The method includes the transfer of highly oxidized americium from an acidic aqueous feed solution through an immobilized liquid membrane to an organic receiving solvent, for example tributyl phosphate. The immobilized liquid membrane includes porous support and separating layers loaded with tributyl phosphate. The extracted solution is subsequently stripped of americium and recycled at the immobilized liquid membrane as neat tributyl phosphate for the continuous extraction of americium. The sequestered americium can be used as a nuclear fuel, a nuclear fuel component or a radiation source, and the remaining constituent elements in the aqueous feed solution can be stored in glassified waste forms substantially free of americium.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Trends in Unconventional Well Development—Methane Emissions Associated with the Use of Dual Fuel and Dedicated Natural Gas Engines

Abstract The process of unconventional natural gas recovery is becoming increasingly popular as the world’s demand for alternative fuels continues to grow. Natural gas has the potential to be a widely used fuel in the near future due to its availability and potential to displace petroleum‐based liquid fuels. As energy companies extract natural gas, current fuels, such as diesel, are consumed in mass quantities for drilling and hydraulic fracturing operations. To save on costs, and in an attempt to reduce emissions, many companies are investing in dual fuel and dedicated natural gas engines to power these operations. This trend results in new sources of methane emissions, which can contribute significantly to global warming. We are aware of the potential impact of these emissions and are conducting research funded by the Department of Energy to assess methane emissions from dual fuel and dedicated natural gas technologies, as industry moves towards more extensive use of natural gas as a fuel for onsite power production.

Johnson, Derek↗

Integrated laser ablation-dropletProbe-mass spectrometry for absolute drug quantitation, metabolite detection, and distribution in tissue

Rationale: Spatially resolved and accurate quantitation of drug-related compounds in tissue is a much-needed capability in drug discovery research. In this work, application of an integrated laser ablation-dropletProbe-mass spectrometry surface sampling system (LADP-MS) is reported, which achieved absolute quantitation of propranolol measured from <500 × 500 μm thin tissue samples. Methods: Mouse liver and kidney thin tissue sections were coated with parylene C and analyzed for propranolol by a laser ablation/liquid extraction workflow. Non-coated adjacent sections were microdissected for validation and processed using standard bulk tissue extraction protocols. High-performance liquid chromatography with positive ion mode electrospray ionization tandem mass spectrometry was applied to detect the drug and its metabolites. Results: Absolute propranolol concentration in ~500 × 500 μm tissue regions measured by the two methods agreed within ±8% and had a relative standard deviation within ±17%. Quantitation down to ~400 × 400 μm tissue regions was shown, and this resolution was also used for automated mapping of propranolol and phase II hydroxypropranolol glucuronide metabolites in kidney tissue. Conclusions: This study exemplifies the capabilities of integrated laser ablation-dropletProbe-mass spectrometry (LADP-MS) for high resolution absolute drug quantitation analysis of thin tissue sections. This capability will be valuable for applications needing to quantitatively understand the spatial distribution of small molecules in tissue.

47 OTHER INSTRUMENTATION↗

Additive Manufacturing: Assessing Metal Powder Quality Through Characterizing Feedstock and Contaminants

The quality of powder feedstock for additive manufacturing (AM) metal powder bed fusion methods can significantly affect the quality of parts built from it. Particle size distribution (PSD) and shape factors influence flowability as well as the thickness and uniformity of each powder layer in the build box. For high-performance applications such as aerospace, medical, power generation and military, it becomes important to identify critical additional factors: the types, numbers and sizes of particulate contaminants that may be present in the powder. This is true for virgin, used and blended powders. Contaminants may be introduced during powder manufacture (e.g., ceramic insulation fragments from gas atomization equipment), handling (building insulation, talc) or possibly during the build process itself. Contaminants contained within a batch of powder can be physically built into an additive part when they are incorporated into the melt pool, and they can remain as discrete particulates or non-fused interfaces that act as stress concentrators. Their presence may decrease fatigue life by increasing the likelihood of fatigue crack initiation. This article describes three methods to rapidly and quantifiably characterize powder feedstock. (1) Computer-controlled scanning electron microscopy (CCSEM) provides quantitative size and shape parameters, as well as fine surface details from individual images on a particle-by-particle basis in large populations of powder. (2) Energy-dispersive spectroscopy (EDS) can be included, providing insights into variations within a batch of powder, as well as contaminant compositions. (3) For critical applications, the heavy liquid separation (HLS) method physically extracts low-density contaminants from a sample of powder metal down to part-per-billion detection limits to allow direct examination of contaminants and enhance identification and prevention of their sources. Altogether, these methods permit direct comparisons among powder metal samples. Better quantification of powder characteristics aids determination of suitability for end uses.

36 MATERIALS SCIENCE↗

Urinary concentrations of environmental phenols in pregnant women in a pilot study of the National Children's Study

Environmental phenols are a group of chemicals with widespread uses in consumer and personal care products, food and beverage processing, and in pesticides. We assessed exposure to benzophenone-3, bisphenol A (BPA), triclosan, methyl- and propyl parabens, and 2,4- and 2,5-dichlorophenol or their precursors in 506 pregnant women enrolled in the National Children's Study (NCS) Vanguard Study. We measured the urinary concentrations of the target phenols by using online solid-phase extraction–isotope dilution high performance liquid chromatography–tandem mass spectrometry. NCS women results were compared to those of 524 similar-aged women in the National Health and Nutrition Examination Survey (NHANES) 2009–2010, and to 174 pregnant women in NHANES 2005–2010. In the NCS women, we found significant racial/ethnic differences (p<0.05) in regression adjusted mean concentrations of benzophenone-3, triclosan, 2,4- and 2,5-dichlorophenol, but not of BPA. Urinary 2,4- and 2,5-dichlorophenol concentrations were highly correlated (r=0.66, p<0.0001). Except for BPA and triclosan, adjusted mean concentrations were significantly different across the 7 study sites. Education was marginally significant for benzophenone-3, triclosan, propyl paraben, and 2,5-dichlorophenol. Urinary concentrations of target phenols in NCS pregnant women and U.S. women and pregnant women were similar. In NCS pregnant women, race/ethnicity and geographic location determined urinary concentrations of most phenols (except BPA), suggesting differential exposures. NCS Main Study protocols should collect urine biospecimens and information about exposures to environmental phenols. - Highlights: • Limited biomonitoring data are available in pregnant women. • Seven urinary phenols were measured in 506 third trimester women enrolled in the NCS. • Urine benzophenone-3, triclosan, 2,4- and 2,5-dichlorophenol differed by race/ethnicity. • Urinary concentrations of 2,4- and 2,5-dichlorophenol were highly correlated. • Exposure information can expand the utility of biospecimens in the NCS Main Study.

54 ENVIRONMENTAL SCIENCES↗

Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ', N ", N "-tetraacetic Acid

Potentiometric and spectroscopic techniques were combined with DFT calculations to probe the coordination environment and determine thermodynamic features of trivalent f-element complexation by N-hydroxyethyl-diethylenetriamine-N,N',N",N"-tetraacetic acid, HEDTTA. Ligand protonation constants and lanthanide stability constants were determined using potentiometry. Five protonation constants were accessible in I = 2.0 M (H + /Na + )ClO 4 . UV–vis spectroscopy was used to determine stability constants for Nd 3+ and Am 3+ complexation with HEDTTA. Luminescence spectroscopy indicates two water molecules in the inner coordination sphere of the Eu/HEDTTA complex, suggesting HEDTTA is heptadentate. Luminescence data was supported by DFT calculations, which demonstrate that substitution of the acetate pendant arm by a N-hydroxyethyl group weakens the metal–nitrogen bond. This bond elongation is reflected in HEDTTA’s ability to differentiate trivalent actinides from trivalent lanthanides. The trans-lanthanide Ln/HEDTTA complex stability trend is analogous to Ln/DTPA complexation; however, the loss of one chelate ring resulting from structural substitution weakens the complexation by ~3 orders of magnitude. Successful separation of trivalent americium from trivalent lanthanides was demonstrated when HEDTTA was utilized as aqueous holdback complexant in a liquid–liquid system. Time-dependent extraction studies for HEDTTA were compared to diethylenetriamine-N,N,N',N",N"-pentaacetic acid (DTPA) and N-hydroxyethyl-ethylenediamine-N,N',N'-triacetic acid (HEDTA). The results presented here indicate substantially enhanced phase-transfer kinetic rates for mixtures containing HEDTTA.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Reorganization Energy of Electron Transfer in Ionic Liquids

We report bandshape analysis of charge-transfer optical bands in room-temperature ionic liquids (ILs) is performed to extract reorganization energy of electron transfer. Remarkably, the reorganization energies in ILs are close to those in cyclohexane. This result runs against common wisdom in the field since conducting ILs, characterized by an infinite static dielectric constant, and nonpolar cyclohexane fall to the opposite ends of the polarity scale based on their dielectric constants. Theoretical calculations employing structure factors of ILs from molecular dynamics simulations support low values of the reorganization energy. Standard dielectric arguments do not apply to solvation in ILs and nonergodic reorganization energies are required for a quantitative analysis.

14 SOLAR ENERGY↗

Non-contacting transfer of elastic energy into explosive simulants for dynamic property estimation

Non-contacting acoustical methods can be used to extract various material properties of liquid or solid samples without disturbing the sample. These methods are useful even in the lab since they do not involve coupling anything to the sample, which might change its properties. A forteriori, when dealing with potentially dangerous materials, non-contacting methods may be the only safe solutions to mechanical characterization. Here, we show examples of using laser ultrasound to remotely insonify and monitor the elastic properties of several granular explosive simulants. The relatively short near-infrared laser pulse length (a few hundred nanoseconds) provides a broad-band thermoelastic source of ultrasound; we intentionally stay in the thermoelastic regime to avoid damaging the material. Then, we use a scanning laser Doppler vibrometer to measure the ultrasonic response of the sample. LDV technology is well established and very sensitive at ultrasonic frequencies; atomic level motions can be measured with modest averaging. The resulting impulse response of the explosive simulant can be analyzed to determine decay rates and wave speeds, with stiffer samples showing faster wave speeds and lower decay rates. On the other hand, at the low-frequency end of the acoustic spectrum, we use an electronically phased array to couple into a freely suspended sample's normal modes. This allows us to gently heat up the sample (3 °C in just under 5 min, as shown with a thermal IR camera). In addition to the practical interest in making the sample more chemically visible through heat, these two measurements (low-frequency resonant excitation vs high-frequency wave propagation) bracket the frequency range of acoustic non-destructive evaluation methods available.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗