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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Thermodynamic modeling of aqueous polyelectrolyte solutions with mixed-valent counterions

Thermodynamic modeling of aqueous polyelectrolyte solutions with salts is of significant interest for many industrial applications. Here this study applies the polyelectrolyte Nonrandom Two-liquid activity coefficient model to aqueous polyelectrolyte solutions with mixed-valent counterions. A modified Delocalized Binding Theory was proposed to determine the polyion condensation fractions of the mixed counterions. This modified theory accounts for the electrostatic binding of the counterions on the polyion, the dissociation entropy of the counterions, and the electrostatic interactions between the uncondensed ionic species. Given the polyion condensation fractions, the critical value of Manning’s parameter ξ and the amounts of uncondensed polyions and counterions can be calculated along with the activity coefficients of mobile ions. The model successfully correlates experimental data for various aqueous polyelectrolyte systems with mixed-valent counterions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Direct and Indirect Reduction of Cr(VI) by Fermentative Fe(III)-Reducing Cellulomonas sp. Strain Cellu-2a

Hexavalent chromium (Cr(VI)) is recognized to be carcinogenic and toxic and registered as a contaminant in many drinking water regulations. It occurs naturally and is also produced by industrial processes. The reduction of Cr(VI) to Cr(III) has been a central topic for chromium remediation since Cr(III) is less toxic and less mobile. In this study, fermentative Fe(III)-reducing bacterial strains (Cellu-2a, Cellu-5a, and Cellu-5b) were isolated from a groundwater sample and were phylogenetically related to species of Cellulomonas by 16S rRNA gene analysis. One selected strain, Cellu-2a showed its capacity of reduction of both soluble iron (ferric citrate) and solid iron (hydrous ferric oxide, HFO), as well as aqueous Cr(VI). The strain Cellu-2a was able to reduce 15 μM Cr(VI) directly with glucose or sucrose as a sole carbon source under the anaerobic condition and indirectly with one of the substrates and HFO in the same incubations. The heterogeneous reduction of Cr(VI) by the surface-associated reduced iron from HFO by Cellu-2a likely assisted the Cr(VI) reduction. Fermentative features such as large-scale cell growth may impose advantages on the application of bacterial Cr(VI) reduction over anaerobic respiratory reduction.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2000

The Hummingbird GC-IMS: In Situ Analysis of a Cometary Nucleus

Comets are of enormous scientific interest for many reasons. They are primitive bodies that date back to the earliest stages of solar system formation and, because of their small size and because they have been stored in the outer reaches of the solar system, their pristine nature has been preserved better than for any other class of body. They are extremely rich in highly volatile elements, many in the form of ices, and are richer in organic matter than any other known solar system body. It is strongly suspected that in addition to their content of primordial solar nebular material, they also incorporate unprocessed matter from the interstellar medium. Impacts by comets occur onto all the planets and satellites, often with major consequences (e.g., the dinosaur extinction event at the KIT boundary), or sometimes just providing a spectacular cosmic event (e.g., the collision of comet Shoemaker-Levy 9 with Jupiter). A mission to analyze a cometary nucleus must be capable of detecting and identifying over 30 molecular species among several different chemical groups. The Hummingbird Mission will rendezvous with, orbit, characterize, and make multiple descents to the nucleus of a comet. Hummingbird will employ a Gas Chromatograph - Ion Mobility Spectrometer (GC-IMS) as part-of a suite of sophisticated instruments for a comprehensive in situ elemental, molecular, and isotopic analysis of the comet.

Kojiro, Daniel R.↗
NASA NTRS2003

MMIC HEMT Power Amplifier for 140 to 170 GHz

A three-stage monolithic microwave integrated circuit (MMIC) power amplifier that features high-electron-mobility transistors (HEMTs) as gain elements is reviewed. This amplifier is designed to operate in the frequency range of 140 to 170 GHz, which contains spectral lines of several atmospheric molecular species plus subharmonics of other such spectral lines. Hence, this amplifier could serve as a prototype of amplifiers to be incorporated into heterodyne radiometers used in atmospheric science. The original intended purpose served by this amplifier is to boost the signal generated by a previously developed 164-GHz MMIC HEMT doubler and drive a 164-to-328-GHz doubler to provide a few milliwatts of power at 328 GHz.

Samoska, Lorene↗
DOE OSTI2024

Advancing Heteroanionicity in Zintl Phases: Crystal Structures, Thermoelectric and Magnetic Properties of Two Quaternary Semiconducting Arsenide Oxides, Eu 8 Zn 2 As 6 O and Eu 14 Zn 5 As 12 O

Two novel quaternary oxyarsenides, Eu 8 Zn 2 As 6 O and Eu 14 Zn 5 As 12 O, were synthesized through metal flux reactions, and their crystal structures were established by single-crystal X-ray diffraction methods. Eu 8 Zn 2 As 6 O crystallizes in the orthorhombic space group Pbca, featuring polyanionic ribbons composed of corner-shared triangular [ZnAs 3 ] units, running along the [100] direction. The structure of Eu 14 Zn 5 As 12 O crystallizes in the monoclinic space group P2/m and its anionic substructure can be described as an infinite “ribbonlike” chain comprised of [ZnAs 3 ] trigonal-planar units, although the structural complexity here is greater and also amplified by disorder on multiple crystallographic positions. In both structures, the O 2– anion occupies an octahedral void with six neighboring Eu 2+ cations. Formal electron counting, electronic structure calculations, and transport properties reveal the charge-balanced semiconducting nature of these heteroanionic Zintl phases. High-temperature thermoelectric transport properties measurements on Eu 14 Zn 5 As 12 O reveal relatively high resistivity (ρ 500K = 8 Ω·cm) and Seebeck coefficient values (S 500K = 220 μV K –1 ), along with a low concentration and mobility of holes as the dominant charge-carriers (n 500K = 8.0 × 10 17 cm –3 , μ 500K = 6.4 cm 2 /V s). Magnetic studies indicate the presence of divalent Eu 2+ species in Eu 14 Zn 5 As 12 O and complex magnetic ordering, with two transitions observed at T 1 = 21.6 K and T 2 = 9 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Investigations towards incorporation of Eu 3+ and Cm 3+ during ZrO 2 crystallization in aqueous solution

Nuclear energy provides a widely applied carbon-reduced energy source. Following operation, the spent nuclear fuel (SNF), containing a mixture of radiotoxic elements such as transuranics, needs to be safely disposed of. Safe storage of SNF in a deep geological repository (DGR) relies on multiple engineered and natural retention barriers to prevent environmental contamination. In this context, zirconia (ZrO 2 ) formed on the SNF rod cladding, could be employed as an engineered barrier for immobilization of radionuclides via structural incorporation. This study investigates the incorporation of Eu 3+ and Cm 3+ , representatives for trivalent transuranics, into zirconia by co-precipitation and crystallization in aqueous solution at 80 °C. Complementary structural and microstructural characterization has been carried out by powder X-ray diffraction (PXRD), spectrum imaging analysis based on energy-dispersive X-ray spectroscopy in scanning transmission electron microscopy mode (STEM-EDXS), and luminescence spectroscopy. The results reveal the association of the dopants with the zirconia particles and elucidate the presence of distinct bulk and superficially incorporated species. Hydrothermal aging for up to 460 days in alkaline media points to great stability of these incorporated species after initial crystallization, with no indication of phase segregation or release of Eu 3+ and Cm 3+ over time. These results suggest that zirconia would be a suitable technical retention barrier for mobilized trivalent actinides in a DGR.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

Final Technical Report for DE-SC0022206

This project developed foundational genetic, genomic, and epigenetic tools for anaerobic fungi (Neocallimastigomycota), a group of microorganisms with exceptional natural abilities to deconstruct lignocellulosic biomass. Efficient biomass deconstruction remains a major barrier to economical production of renewable fuels, chemicals, and materials from agricultural and forestry residues. The project sought to enable mechanistic studies and future engineering of anaerobic fungi by improving genomic resources, establishing methods for gene expression, and investigating epigenetic regulation of biomass-degrading pathways. Major accomplishments included generation of the first chromosome-scale genome assemblies for multiple anaerobic fungal species, providing publicly available genomic resources that support both engineering and fundamental biological research. The project established the first reproducible system for heterologous gene expression in anaerobic fungi and identified genomic features and mobile genetic elements that may support future development of stable transformation technologies. In parallel, the project demonstrated direct conversion of untreated lignocellulosic biomass into fuels and specialty chemicals through a fungal-yeast bioprocess and identified anaerobic fungal enzymes with utility for metabolic engineering. The research also revealed that epigenetic regulation plays an important role in controlling fungal gene expression and enzyme production, identifying potential strategies for enhancing biomass degradation. Collectively, this work established anaerobic fungi as a tractable emerging platform for bioenergy and biomanufacturing research, generated valuable public resources, trained the next generation of researchers, and advanced DOE-BER goals related to predictive biology, sustainable bioprocessing, and the circular bioeconomy.

Solomon, Kevin [University of Delaware] (ORCID:000↗
DOE OSTI2023

Sr 2 Fe 2–X Mo X O 6 double perovskites as electrocatalysts for oxidative dehydrogenation of ethane: Effect of B-site stoichiometry

The oxidative dehydrogenation of ethane (ODHE) was investigated using a solid oxide electrocatalytic cell with Sr 2 Fe 2–X Mo X O 6–δ (SFM) double perovskite as the anode electrocatalyst. As shown in the XRD patterns, SFM perovskites maintained their cubic structure upon modifying the B-site ratios of Mo and Fe. Increasing the Mo content of the perovskite structure resulted in a lower water signal intensity at low temperatures in TPR profiles, indicative of moderate oxygen transport through the perovskite structure. Because Mo–O bonds are stronger than Fe–O bonds, the electrical conductivity of SFM perovskites decreased with increasing Mo content. When operated at 100 mA cm –2 , ODHE activity improved four times compared to open circuit voltage, resulting in 16.1% conversion of C 2 H 6 and 83.1% selectivity to C 2 H 4 . It has been demonstrated that oxygen ions provided by perovskite lattices were the key species involved in activating C 2 H 6 based on the in-situ DRIFTS experiments. In conclusion, the SFM perovskite with higher Mo content showed the highest conversion and selectivity due moderate oxygen ion mobility and fast desorption of C 2 H 4 .

25 ENERGY STORAGE↗
DOE OSTI2025

Spectroscopic Investigation into P(NDI2OD-T2) Charge Localization

P(NDI2OD-T2), commonly referred to as N2200, stands out as a promising electron-transporting (n-type) polymer for low-cost, flexible (photo)electrochemical applications due to its reversible two-electron reduction and high electron mobility. UV–vis spectroelectrochemistry in the tetrabutyl ammonium hexafluorophosphate/acetonitrile electrolyte shows two sets of chemically reversible redox signals in the cyclic voltammetry corresponding to the reduction of the neutral polymer film to polaronic and bipolaronic species. These electrochemical signatures suggest a distinct electronic reorganization upon reduction (polaron/bipolaron formation), highlighting the need for molecular-level insights into how charges are accommodated within the polymer backbone. While it has been previously hypothesized that charge predominantly localizes on the naphthalene diimide (NDI) unit during reductive charging, specific changes in atomic environments that confirm this localization have not been characterized in n-type polymers. Herein, we use near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to probe electronic transitions in an electrochemically charged polymer to deduce charge localization. The O K-edge (1s) spectra exhibit two distinct π* peaks; the intensity of the lower-energy π* a peak that corresponds to an excitation to a largely localized carbonyl state decreases with reductive potentials relative to the higher-energy π* b peak. We corroborate this with Raman spectroscopy at different potentials, which shows a decrease in intensity on the C–C/C═C and C═O stretching bands of NDI as well as a red shift of the carbonyl band due to the formation of a polaron on the NDI. Additionally, new Raman active NDI signals associated with elongated C═O and C═C bonds are observed at lower energy during the formation of charged states. Together with theoretical calculations, these findings show that the injected charge spatially localizes on the NDI units and is dominantly distributed on the carbonyl groups. In conclusion, the combination of NEXAFS, optical and vibrational spectroscopies, and theoretical calculations is generalizable to other pi-conjugated polymers and can identify charge localization for the further development of organic semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Transport and Energetics of Carbon Dioxide in Ionic Liquids at Aqueous Interfaces

A major hurdle in utilizing carbon dioxide (CO 2 ) lies in separating it from industrial flue gas mixtures and finding suitable storage methods that enable its application in various industries. To address this issue, we utilized a combination of molecular dynamics simulations and experiments to investigate the behavior of CO 2 in common room-temperature ionic liquids (RTIL) when in contact with aqueous interfaces. Here, our investigation of RTILs, [EMIM][TFSI] and [OMIM][TFSI], and their interaction with a pure water layer mimics the environment of a previously developed ultrathin enzymatic liquid membrane for CO 2 separation. We analyzed diffusion constants and viscosity, which reveals that CO 2 molecules exhibit faster mobility within the selected ILs compared to what would be predicted solely based on the viscosity of the liquids using the standard Einstein–Stokes relation. Moreover, we calculated the free energy of translocation for various species across the aqueous–IL interface, including CO 2 and HCO 3 – . Free energy profiles demonstrate that CO 2 exhibits a more favorable partitioning behavior in the RTILs compared to that in pure water, while a significant barrier hinders the movement of HCO 3 – from the aqueous layer. Experimental measurement of the CO 2 transport in the RTILs corroborates the model. These findings strongly suggest that hydrophobic RTILs could serve as a promising option for selectively transporting CO 2 from aqueous media and concentrating it as a preliminary step toward storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Optimizing the electron transport chain to sustainably improve photosynthesis

Abstract Genetically improving photosynthesis is a key strategy to boosting crop production to meet the rising demand for food and fuel by a rapidly growing global population in a warming climate. Many components of the photosynthetic apparatus have been targeted for genetic modification for improving photosynthesis. Successful translation of these modifications into increased plant productivity in fluctuating environments will depend on whether the electron transport chain (ETC) can support the increased electron transport rate without risking overreduction and photodamage. At present atmospheric conditions, the ETC appears suboptimal and will likely need to be modified to support proposed photosynthetic improvements and to maintain energy balance. Here, I derive photochemical equations to quantify the transport capacity and the corresponding reduction level based on the kinetics of redox reactions along the ETC. Using these theoretical equations and measurements from diverse C3/C4 species across environments, I identify several strategies that can simultaneously increase the transport capacity and decrease the reduction level of the ETC. These strategies include increasing the abundances of reaction centers, cytochrome b6f complexes, and mobile electron carriers, improving their redox kinetics, and decreasing the fraction of secondary quinone–nonreducing photosystem II reaction centers. I also shed light on several previously unexplained experimental findings regarding the physiological impacts of the abundances of the cytochrome b6f complex and plastoquinone. The model developed, and the insights generated from it facilitate the development of sustainable photosynthetic systems for greater crop yields.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Removable, Sequestration Coatings for Mitigating Hazardous Contaminants Related to Deactivation and Decommissioning Activities

This project is a collaborative effort between InnoSense LLC (ISL) and Oak Ridge National Laboratory (ORNL) aimed at mitigating the mercury (Hg) contamination problem at the Y-12 National Security Complex (NSC). The report summarizes the research and technology development work of the Phase IIB Project, led by Dr. Uma Sampathkumaran at ISL for the period of July 31, 2017–October 31, 2021. The Y-12 site cleanup includes technologies for safe and cost-effective facility demolition, soil remediation, and on-site treatment and disposal of mercury bearing wastes. One of the technology demonstration goals was a reactive strippable coating for targeted pre-demolition and de-contamination to limit Hg mobilization and the volume of debris requiring treatment for disposal. Toward this, ISL has developed a water-based reactive strippable coating (Trap & See-Hg™) to sequester elemental Hg(0) and mercuric Hg(II) species in the coating. The coating provides multiple benefits including (1) Hg vapor suppression, (2) sealing in the hazardous contaminants, (3) visually locating the contaminant through color changes, and (4) remediating the contaminated surfaces upon coating removal. Through collaboration between ORNL and ISL in Phase II work, the team successfully demonstrated the Trap & See-Hg technology to (1) visually locate the presence of Hg on concrete, soil and drywall surfaces, (2) effectively sequester all mercury species (elemental, soluble and insoluble Hg) from lab-generated and ex-situ soil and brick/rubble samples collected from the Y 12 site with 80 to 95% efficiency to capture/reduce Hg vapor concentration, (3) be applied by manual and robotic spray applicators and cure at room ambient, (4) remain a cohesive and peelable coating upon drying, and (5) sequester Hg0 from walls in the alpha-2 building basement at Y-12 during a small scale in-situ field trial. In Phase IIB, ISL’s effort was focused on refining the coating formulations with additives containing passive and reactive sorbents, colorimetric indicator, and thixotropic agents to achieve the desired performance. The paints were then evaluated at ORNL for applicability to metal and concrete surfaces of different sizes and shapes, and soil rubble, Hg-sorption capacity and achieving sag-free coating on surfaces when applied by a manual spray applicator. Ambient cure of the coating resulted in a dry thickness of 16–20 mil. The coatings were removed from smooth or rough surfaces with low to moderate force. Both lab-generated Hg-contaminated samples and soil and brick/rubble samples containing a range of Hg concentrations (collected from the Y-12 site by UCOR) were used in this project. Optimized formulations were applied to these samples and evaluated for ability to suppress Hg vapors, sequester Hg 0 and Hg(II) species and color mapping of mercury species on the test surface. The ORNL team initially identified three to four potential sites at Y-12 and ORNL for potential demonstration. However, the pandemic closed any possible avenues for on-site demonstration of the robotic spray applicator. The metal and concrete samples with low to high Hg content provided by UCOR from an ongoing demolition were subsequently used for ex-situ sample characterization and analysis at ORNL over a period of 25 days. The coatings suppressed Hg vapors with an efficiency of 95–99% from heavily contaminated metal and 60% from concrete substrate. Analysis of total Hg in the peeled paints indicates sorption capacities ranging from 12 µg Hg/g of paint from concrete to 1.2 mg Hg/g of paint from the metal substrates while peeled paints from soil samples could capture a total Hg from 2.3 mg Hg/g to 66 mg/g paint. Toxicity characteristic leaching procedure (TCLP) tests recovered total mercury leached at 0.15±0.0008 µg/L for concrete to 126.81±0.67 µg/L and 377.25±5.67 µg/L for the two metal substrates, to allow for informed decisions on downstream disposal considerations. Together, this Phase IIB demonstrated the potential value of the Trap & See-Hg for Hg uptake, vapor suppression, and color mapping, and may thus be used to enhance worker safety during site cleanup, facility demolition, and downstream waste disposal at Y-12 NSC.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Hydrothermal solubility of Dy hydroxide as a function of pH and stability of Dy hydroxyl aqueous complexes from 25 to 250 °C

The rare earth elements (REE) have important applications in green energy technologies. The formation of mineral deposits in geologic systems commonly involves hydrothermal fluids which can mobilize the REE. However, the REE speciation is not well known as a function of pH. The thermodynamic properties of REE hydroxyl complexes used in geochemical models are based on the Helgeson-Kirkham-Flowers (HKF) equation of state parameters which were derived by extrapolation of low temperature experimental and estimated data. In this study, Dy hydroxide solubility experiments are combined with available literature data to improve these models from 25 to 250 °C and optimize the thermodynamic properties of Dy 3+ and Dy hydroxyl complexes using GEMSFITS. Batch-type solubility experiments were conducted from 150 to 250 °C and at saturated water vapor pressure in perchloric acid solutions with initial pH values of 2 to 5 in 0.5 pH unit increments. The measured solubility of Dy hydroxide is retrograde with temperature and decreases with pH. The logarithm of total dissolved Dy molality ranges from –2.3 to –5.3 at 150 °C (pH 4.7–5.5), from –2.4 to –5.6 at 200 °C (pH 3.9–5.1), and from –3.7 to –6.9 at 250 °C (pH of 3.4 and 5.0). The optimized standard partial molal Gibbs energies of formation (Δ f G° T ) derived for Dy 3+ and DyOH 2+ display a close to linear relationship with temperature, fitting with previous optimizations based on DyPO 4 solubility data in the literature. A comparison of the optimized ΔfG°T values for aqueous Dy species with predictions from available HKF parameters indicates significant differences ranging from +11 to –26 kJ/mol between 25 and 250 °C. The experimental fits are used to derive the Dy hydroxide solubility products (K s0 ) and formation constants for the hydrolysis of Dy (β n with n = 1 to 3; Dy 3+ + nOH – = DyOH n 3-n ) as a function of temperature. The optimization method presented yields accurate thermodynamic properties for the Dy 3+ aqua ions and the DyOH 2+ species at the acidic to mildly acidic pH studied whereas more experimental work is needed at near-neutral and alkaline conditions to better constrain the other hydroxyl complexes. Furthermore, the optimized thermodynamic data have a significant impact on geochemical modeling of the mobility and solubility of REE minerals in acidic hydrothermal fluids.

58 GEOSCIENCES↗
DOE OSTI2022

Ionic Tunability of Conjugated Polyelectrolyte Solutions

Conjugated polyelectrolytes (CPEs), which combine a π-conjugated polymer backbone with pendant ionic functionalities, offer an opportunity for electrostatic control of materials properties. In this work, the mesoscale morphology and physical properties of a high-mobility conjugated polyelectrolyte are tuned by the addition of salt, variation of the charge-compensating counterion, and complexation with an oppositely charged polyelectrolyte containing the same π-conjugated backbone. In systems with a single polyelectrolyte species, added ions screen the electrostatic repulsions stabilizing the gel-phase, resulting in the dissolution of ionic cross-links and hydrophobic collapse. Further, exchanging the charge compensating counterion is found to enable finer structural control of the solution behavior and modulation of the self-doping behavior. Finally, novel CPE–CPE complexes resulting in dense solutions and gels of semiconductive material are produced by combination of oppositely charged polyelectrolytes. Such concentrated CPE formulations should be useful materials for mixed electronic–ionic conduction and pseudocapacitative energy storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1991

Analysis of model Titan atmospheric components using ion mobility spectrometry

The Gas Chromatograph-Ion Mobility Spectrometer (GC-IMS) was proposed as an analytical technique for the analysis of Titan's atmosphere during the Cassini Mission. The IMS is an atmospheric pressure, chemical detector that produces an identifying spectrum of each chemical species measured. When the IMS is combined with a GC as a GC-IMS, the GC is used to separate the sample into its individual components, or perhaps small groups of components. The IMS is then used to detect, quantify, and identify each sample component. Conventional IMS detection and identification of sample components depends upon a source of energetic radiation, such as beta radiation, which ionizes the atmospheric pressure host gas. This primary ionization initiates a sequence of ion-molecule reactions leading to the formation of sufficiently energetic positive or negative ions, which in turn ionize most constituents in the sample. In conventional IMS, this reaction sequence is dominated by the water cluster ion. However, many of the light hydrocarbons expected in Titan's atmosphere cannot be analyzed by IMS using this mechanism at the concentrations expected. Research at NASA Ames and PCP Inc., has demonstrated IMS analysis of expected Titan atmospheric components, including saturated aliphatic hydrocarbons, using two alternate sample ionizations mechanisms. The sensitivity of the IMS to hydrocarbons such as propane and butane was increased by several orders of magnitude. Both ultra dry (waterless) IMS sample ionization and metastable ionization were successfully used to analyze a model Titan atmospheric gas mixture.

Kojiro, D. R.↗
NASA NTRS1992

Meiosis, egg activation, and nuclear envelope breakdown are differentially reliant on Ca2+, whereas germinal vesicle breakdown is Ca2+ independent in the mouse oocyte

During early development, intracellular Ca2+ mobilization is not only essential for fertilization, but has also been implicated during other meiotic and mitotic events, such as germinal vesicle breakdown (GVBD) and nuclear envelope breakdown (NEBD). In this study, the roles of intracellular and extracellular Ca2+ were examined during meiotic maturation and reinitiation at parthenogenetic activation and during first mitosis in a single species using the same methodologies. Cumulus-free metaphase II mouse oocytes immediately resumed anaphase upon the induction of a large, transient Ca2+ elevation. This resumption of meiosis and associated events, such as cortical granule discharge, were not sensitive to extracellular Ca2+ removal, but were blocked by intracellular Ca2+ chelators. In contrast, meiosis I was dependent on external Ca2+; in its absence, the formation and function of the first meiotic spindle was delayed, the first polar body did not form and an interphase-like state was induced. GVBD was not dependent on external Ca2+ and showed no associated Ca2+ changes. NEBD at first mitosis in fertilized eggs, on the other hand, was frequently, but not always associated with a brief Ca2+ transient and was dependent on Ca2+ mobilization. We conclude that GVBD is Ca2+ independent, but that the dependence of NEBD on Ca2+ suggests regulation by more than one pathway. As cells develop from Ca(2+)-independent germinal vesicle oocytes to internal Ca(2+)-dependent pronuclear eggs, internal Ca2+ pools increase by approximately fourfold.

Non-NASA Center↗
DOE OSTI2021

The solubility of thorium in carbonate-bearing solutions at hydrothermal conditions

Thorium mineralization is frequently hosted in carbonate-bearing rocks, and thorium commonly substitutes into the structures of carbonate-bearing minerals that have precipitated from or been modified by hydrothermal fluids. Given this common association, it is reasonable to consider the hypothesis that the presence of carbonate ligands in hydrothermal solutions promotes the transport of Th through the formation of stable aqueous complexes. Our ability to evaluate this hypothesis, however, is hindered by the lack of experimental data for Th-carbonate species at conditions beyond ambient. The low-temperature data indicate that carbonate is a strong complexing agent for Th. In this contribution, we investigate the solubility of Th in carbonate-bearing fluids relevant to natural systems (0.05–0.5 m NaHCO 3 /Na 2 CO 3 ; pH T ~ 7.8–9.8) at elevated temperature (175–250 °C). We demonstrate that, in contrast to the behavior of Th at low temperature, the stability of Th-carbonate complexes is not sufficient for them to predominate at these conditions. Instead, the solubility of Th is governed by hydrolysis reactions. Under the experimental conditions investigated, the predominant hydroxyl complexes are Th(OH) 4 0 and Th(OH) 5 -. Furthermore, thermodynamic formation constants were derived for these species at the temperatures considered in our experiments (log β 4 = 43.34 and 44.31 at 175 and 200 °C, respectively, and log β 5 = 46.15 and 47.9 at 225 and 250 °C, respectively) to permit forward modeling of Th mobility in natural systems. Our study indicates that carbonate ions are unlikely to play a role in transporting Th in hydrothermal fluids. Summarizing the results of this study and our previous studies of the solubility of Th in hydrothermal fluids, we conclude that SO 4 2- is the primary ligand responsible for the hydrothermal transport of Th.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Apolipoprotein A-I modulates HDL particle size in the absence of apolipoprotein A-II

Human high-density lipoproteins (HDLs) are a complex mixture of structurally related nanoparticles that perform distinct physiological functions. We previously showed that human HDL containing apolipoprotein A-I (APOA1) but not apolipoprotein A-II (APOA2), designated LpA-I, is composed primarily of two discretely sized populations. Here, we isolated these particles directly from human plasma by antibody affinity chromatography, separated them by high-resolution size-exclusion chromatography and performed a deep molecular characterization of each species. The large and small LpA-I populations were spherical with mean diameters of 109 Å and 91 Å, respectively. Unexpectedly, isotope dilution MS/MS with [ 15 N]-APOA1 in concert with quantitation of particle concentration by calibrated ion mobility analysis demonstrated that the large particles contained fewer APOA1 molecules than the small particles; the stoichiometries were 3.0 and 3.7 molecules of APOA1 per particle, respectively. MS/MS experiments showed that the protein cargo of large LpA-I particles was more diverse. Human HDL and isolated particles containing both APOA1 and APOA2 exhibit a much wider range and variation of particle sizes than LpA-I, indicating that APOA2 is likely the major contributor to HDL size heterogeneity. We propose a ratchet model based on the trefoil structure of APOA1 whereby the helical cage maintaining particle structure has two “settings”—large and small—that accounts for these findings. This understanding of the determinants of HDL particle size and protein cargo distribution serves as a basis for determining the roles of HDL subpopulations in metabolism and disease states.

59 BASIC BIOLOGICAL SCIENCES↗