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At least 469 records · Page 26

Correlation of Helium Solubility in Liquid Nitrogen

A correlation has been developed for the equilibrium mole fraction of soluble gaseous helium in liquid nitrogen as a function of temperature and pressure. Experimental solubility data was compiled and provided by National Institute of Standards and Technology (NIST). Data from six sources was used to develop a correlation within the range of 0.5 to 9.9 MPa and 72.0 to 119.6 K. The relative standard deviation of the correlation is 6.9 percent.

VanDresar, Neil T.↗

Evaluation of the Maximum Soluble Water Recovery from Pretreated Urine Brines in Low Earth Orbit

The Urine Processor Assembly (UPA) on the International Space Station recovers water from pretreated urine by thin-film, vacuum compression distillation (VCD). A number of iterative improvements to the distiller assembly (DA) have enabled increases in on-orbit water recovery and improved distillate water quality at on-orbit recoveries up to 87% by volume relative to the volume of pretreated urine. The phosphoric acid-based pretreatment formulation has enabled these higher recoveries on-orbit since May of 2016. Application of simple empirical chemistry models have allowed water recovery of sulfuric-acid pretreated urine from the Russian Orbiting segment to be distilled with phosphoric acid pretreated urine from the U.S. Orbiting Segment. Returned liquid brine from brine filters in the UPA brine loop have enabled empirical measurement of gypsum solubility as a function of recovery, conductivity, or mass density in the real brines of ISS. Calculations of maximum soluble recovery, MSR, are based on preventing the precipitation of gypsum, which is the first mineral to precipitate for both types of pretreated urine. A statistical urine model of urine composition provides an estimate of worst-case urine from a crew of three during one year of operations on ISS. The MSR is defined based on the worst-case concentrations of urinary calcium and urinary sulfate that are pretreated, pooled, and distilled. The potential to increase water recoveries above 87% without gypsum precipitation are evaluated. The potential benefits and costs of the addition of a conductivity sensor or a Coriolis mass flow meter to the brine loop are evaluated.

Dean L Muirhead↗

The Spatial Distribution of Soluble Organic Matter and Their Relationship to Minerals in the Asteroid (162173) Ryugu

We performed in-situ analysis on a ~1 mm-sized grain A0080 returned by the Hayabusa2 spacecraft from near-Earth asteroid (162173) Ryugu to investigate the relationship of soluble organic matter (SOM) to minerals. Desorption electrospray ionization-high resolution mass spectrometry (DESI-HRMS) imaging mapped more than 200 CHN, CHO, CHO–Na (sodium adducted), and CHNO soluble organic compounds. A heterogeneous spatial distribution was observed for different compound classes of SOM as well as among alkylated homologues on the sample surface. The A0080 sample showed mineralogy more like an Ivuna-type (CI) carbonaceous chondrite than other meteorites. It contained two different lithologies, which are either rich (lithology 1) or poor (lithology 2) in magnetite, pyrrhotite, and dolomite. CHN compounds were more concentrated in lithology 1 than in lithology 2; on the other hand, CHO, CHO–Na, and CHNO compounds were distributed in both lithologies. Such different spatial distribution of SOM is likely the result of interaction of the SOM with minerals, during precipitation of the SOM via fluid activity, or could be due to difference in transportation efficiencies of SOMs in aqueous fluid. Organic-related ions measured by time-of-flight secondary ion mass spectrometry (ToF–SIMS) did not coincide with the spatial distribution revealed by DESI-HRMS imaging. This result may be because the different ionization mechanism between DESI and SIMS, or indicate that the ToF–SIMS data would be mainly derived from methanol-insoluble organic matter in A0080. In the Orgueil meteorite, such relationship between altered minerals and SOM distributions was not observed by DESI-HRMS analysis and field-emission scanning electron microscopy, which would result from differences of SOM formation processes and sequent alteration process on the parent bodies or even on the Earth. Alkylated homologues of CHN compounds were identified in A0080 by DESI-HRMS imaging as observed in the Murchison meteorite, but not from the Orgueil meteorite. These compounds with a large C number were enriched in Murchison fragments with abundant carbonate grains. In contrast, such relationship was not observed in A0080, implying different formation or growth mechanisms for the alkylated CHN compounds by interaction with fluid and minerals on the Murchison parent body and asteroid Ryugu.

Ryugu↗

Soluble Organic Matter Molecular Atlas of Ryugu Reveals Cold Hydrothermalism on C-Type Asteroid Parent Body

The sample from the near-Earth carbonaceous asteroid (162173) Ryugu is analyzed in the context of carbonaceous meteorites soluble organic matter. The analysis of soluble molecules of samples collected by the Hayabusa2 spacecraft shines light on an extremely high molecular diversity on the C-type asteroid. Sequential solvent extracts of increasing polarity of Ryugu samples are analyzed using mass spectrometry with complementary ionization methods and structural information confirmed by nuclear magnetic resonance spectroscopy. Here we show a continuum in the molecular size and polarity, and no organomagnesium molecules are detected, reflecting a low temperature and water-rich environment on the parent body approving earlier mineralogical and chemical data. High abundance of sulfidic and nitrogen rich compounds as well as high abundance of ammonium ions confirm the water processing. Polycyclic aromatic hydrocarbons are also detected in a structural continuum of carbon saturations and oxidations, implying multiple origins of the observed organic complexity, thus involving generic processes such as earlier carbonization and serpentinization with successive low temperature aqueous alteration.

Asteroids, comets and Kuiper belt↗

Primordial Aqueous Alteration Recorded in Water-Soluble Organic Molecules from the Carbonaceous Asteroid (162173) Ryugu

We report primordial aqueous alteration signatures in water-soluble organic molecules from the carbonaceous asteroid (162173) Ryugu by the Hayabusa2 spacecraft of JAXA. Newly identified low-molecular-weight hydroxy acids (HO-R-COOH) and dicarboxylic acids (HOOC-R-COOH), such as glycolic acid, lactic acid, glyceric acid, oxalic acid, and succinic acid, are predominant in samples from the two touchdown locations at Ryugu. The quantitative and qualitative profiles for the hydrophilic molecules between the two sampling locations shows similar trends within the order of ppb (parts per billion) to ppm (parts per million). A wide variety of structural isomers, including α- and β-hydroxy acids, are observed among the hydrophilic molecules. We also identify pyruvic acid and dihydroxy and tricarboxylic acids, which are biochemically important intermediates relevant to molecular evolution, such as the primordial TCA (tricarboxylic acid) cycle. Here, we find evidence that the asteroid Ryugu samples underwent substantial aqueous alteration, as revealed by the presence of malonic acid during keto–enol tautomerism in the dicarboxylic acid profile. The comprehensive data suggest the presence of a series for water-soluble organic molecules in the regolith of Ryugu and evidence of signatures in coevolutionary aqueous alteration between water and organics in this carbonaceous asteroid.

Asteroids, comets and Kuiper belt↗

Abundant Ammonia and Nitrogen-Rich Soluble Organic Matter in Samples From Asteroid (101955) Bennu

Organic matter in meteorites reveals clues about early Solar System chemistry and the origin of molecules important to life, but terrestrial exposure complicates interpretation. Samples returned from the B-type asteroid Bennu by the Origins, Spectral Interpretation, Resource Identifcation, and Security–Regolith Explorer mission enabled us to study pristine carbonaceous astromaterial without uncontrolled exposure to Earth’s biosphere. Here we show that Bennu samples are volatile rich, with more carbon, nitrogen and ammonia than samples from asteroid Ryugu and most meteorites. Nitrogen-15 isotopic enrichments indicate that ammonia and other N-containing soluble molecules formed in a cold molecular cloud or the outer protoplanetary disk. We detected amino acids (including 14 of the 20 used in terrestrial biology), amines, formaldehyde, carboxylic acids, polycyclic aromatic hydrocarbons and N-heterocycles (including all fve nucleobases found in DNA and RNA), along with ~10,000 N-bearing chemical species. All chiral non-protein amino acids were racemic or nearly so, implying that terrestrial life’s left-handed chirality may not be due to bias in prebiotic molecules delivered by impacts. The relative abundances of amino acids and other soluble organics suggest formation and alteration by low-temperature reactions, possibly in NH3-rich fuids. Bennu’s parent asteroid developed in or accreted ices from a reservoir in the outer Solar System where ammonia ice was stable.

Daniel P Glavin↗

Use Of Stream Analyzer For Solubility Predictions Of Selected Hanford Tank Waste

The Hanford Tank Waste Operations Simulator (HTWOS) models the mission to manage, retrieve, treat and vitrify Hanford waste for long-term storage and disposal. HTWOS is a dynamic, flowsheet, mass balance model of waste retrieval and treatment activities. It is used to evaluate the impact of changes on long-term mission planning. The project is to create and evaluate the integrated solubility model (ISM). The ISM is a first step in improving the chemistry basis in HTWOS. On principal the ISM is better than the current HTWOS solubility. ISM solids predictions match the experimental data well, with a few exceptions. ISM predictions are consistent with Stream Analyzer predictions except for chromium. HTWOS is producing more realistic results with the ISM.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Facilitating protein solubility by use of peptide extensions

Expression vectors for expression of a protein or polypeptide of interest as a fusion product composed of the protein or polypeptide of interest fused at one terminus to a solubility enhancing peptide extension are provided. Sequences encoding the peptide extensions are provided. The invention further comprises antibodies which bind specifically to one or more of the solubility enhancing peptide extensions.

59 BASIC BIOLOGICAL SCIENCES↗

Experimental Determination of Solubilities of Tri-calcium Di-Citrate Tetrahydrate [Ca 3 [C 3 H 5 O(COO) 3 ] 2 •4H 2 O] Earlandite in NaCl and MgCl 2 Solutions to High Ionic Strengths and Its Pitzer Model: Applications to Nuclear Waste Isolation and Other Low Temperature Environments

In this study, solubility measurements on tri-calcium di-citrate tetrahydrate [Ca 3 [C 3 H 5 O(COO) 3 ]2•4H 2 O, abbreviated as Ca 3 [Citrate] 2 •4H 2 O] as a function of ionic strength are conducted in NaCl solutions up to I = 5.0 mol•kg –1 and in MgCl 2 solutions up to I = 7.5 mol•kg –1 , at room temperature (22.5 ± 0.5°C). The solubility constant (log K$0\atop{sp}$) for Ca 3 [Citrate] 2 •4H 2 O and formation constant (logβ$0\atop{1}$) for Ca[C 3 H 5 O(COO) 3 ] – Ca 3 [C 3 H 5 O(COO) 3 ] 2 •4H 2 O (earlandite) = 3Ca 2+ + 2[C 3 H 5 O(COO) 3 ] 3– + 4H 2 O (1) Ca 2+ + [C 3 H 5 O(COO) 3 ] 3– = Ca[C 3 H 5 O(COO) 3 ] – (2) are determined as –18.11 ± 0.05 and 4.97 ± 0.05, respectively, based on the Pitzer model with a set of Pitzer parameters describing the specific interactions in NaCl and M g Cl 2 media.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Membrane Binding of Soluble Enzymes, Explored Through Simulation of Bacterial P450s

Members of the P450 enzyme family catalyze the oxidation of many different, but primarily lipophillic, substrates. In eukaryotic P450s, a membrane-anchored N-terminal helix tethers the enzyme to the membrane. However, in bacterial P450s, no N-terminal helix is present in the sequence, and the proteins are found to be soluble and amenable to solution experiments. Through unbiased classical molecular dynamics simulations, we demonstrate that these soluble enzymes bind to lipid membranes in the same orientation as tethered P450s. We postulate that the observed membrane binding improves the turnover of the enzyme by co-locating the enzyme at regions of high substrate concentration. Through mathematical modeling, we determine that the small cellular volume in prokaryotes is the primary reason that no N-terminal helix is found in these enzymes, as fewer enzymes are mistargeted into the small cytoplasmic space.

09 BIOMASS FUELS↗

Utilization of protein film electrochemistry to characterize the mechanisms imparting aerotolerance and bidirectionality in soluble, multimeric [NiFe]-hydrogenases (Final Report for Grant No. DE-SC0008074)

The overall goal of this project was to better understand how structural features control functional aspects of enzymes involved in catalysis in which a substrate is oxidized or reduced. Two types of model enzymes were explored: the soluble [NiFe]-hydrogenase from Pyrococcus furiousus and the thiosulfate reductase from Pyrobaculum aerophilum. Both are models for complex, multielectron transformations such as nitrogen and carbon dioxide reduction, and parts of important biogeochemical cycles. In this project, electrochemical methods were used to define the activities of these enzymes and targeted variants designed to modulate activity. We showed that the catalytic activity of the soluble hydrogenase from Pyrococcus furiosus can be modulated by removing large parts of the enzyme far from the active site. This surprising result suggests that interactions between functional centers far apart within the enzyme may be essential for controlling and tuning activity. We also showed that the catalytic activity of thiosulfate reductase from Pyrobaculum aerophilum can be modulated by changing the metal at the active site to be either molybdenum or tungsten. These results contribute to our understanding of how the protein environment can tune the reactivity of an embedded metal, catalytic center. The results were and are being published in peer-reviewed, scientific publications.

08 HYDROGEN↗

Use of Solid Pyrex Rod for Conceptual Soluble Boron Free SMR

Various small modular reactor (SMR) designs have been proposed by the nuclear vendors and universities in order to address the energy needs for developing countries and remote communities. Most of them target for the long-term fuel cycle of 4 years or more to achieve high availability. In addition, soluble boron free operation is proposed to simplify the primary system, to enhance the safety characteristics by inherent negative moderator temperature coefficients, etc. The Pyrex rods are used to hold-down the excess reactivity in the core. In order to achieve the cycle length of 4 years, Solid Pyrex rods are used for Conceptual Soluble Boron Free SMR (CSBF-SMR) design. The Solid Pyrex rods which are one of conventional burnable absorbers (BAs) have advantages in the license and applicability into current design of fuel assembly. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

The Effects of Reflector on Core Reactivity for Conceptual Soluble Boron Free SMR

Various small modular reactor (SMR) designs have been proposed by the nuclear vendors and universities in order to address the energy needs for developing countries and remote communities. Most of them target for the long-term fuel cycle of 4 years or more to achieve high availability. In addition, soluble boron free operation is proposed to simplify the primary system, to enhance the safety characteristics by inherent negative moderator temperature coefficients, etc. The neutron economy should be improved to achieve longer cycle length with a small core. Therefore, analysis of reflector for Conceptual Soluble Boron Free SMR. (CSBF-SMR) is required. In this study, five materials for radial reflector were selected to investigate the effect on core reactivity. Their thickness was also analyzed to get an optimum configuration. The goal of this study is to determine optimum material and thickness of reflector of the CSBF-SMR.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Determining the Solubility Behavior of Kogarkoite in Simulated Nuclear Waste

Kogarkoite (Na 3 FSO 4 ) is a sparingly soluble fluoride–sulfate double salt that has been identified in high level nuclear waste sludge at the Hanford Site and, more recently, in sludge batch compilation samples at the Savannah River Site (SRS). Due to its complex dissolution behavior, which exhibits an inverse dependence on sodium ion activity, the presence of this mineral poses significant challenges to waste retrieval and processing. Incomplete dissolution during sludge washing can lead to the retention of fluoride and sulfate in the high-level waste feed, potentially causing the formation of corrosive, immiscible molten salt layers, known as "glass gall,” in vitrification melters. Current efforts to optimize flowsheet parameters and wash-water volumes are hindered by the absence of a commercially available, certified reference material, which prevents the accurate calibration of analytical methods and the verification of dissolution kinetics. To address this critical gap, this research focuses on the laboratory synthesis of pure Kogarkoite to serve as a standard for comprehensive solubility and washing performance testing. A coupled synthesis and simulant campaign was executed using an evaporative crystallization protocol designed to replicate the dynamic concentration effects observed in tank farm operations. Thirteen simulant matrices were prepared by dissolving systematically varied ratios of sodium fluoride (NaF) and sodium sulfate (Na 2 SO 4 ) in deionized water under three distinct caustic regimes: 0.0 g (control), 4.0 g (~1 M), and 12.0 g (~3 M) sodium hydroxide (NaOH). While thermodynamic equilibrium models suggest that high-caustic environments should favor the stability of the double salt7, results from this evaporative study at 25 0 C revealed a distinct kinetic divergence. Simulants with high hydroxide loading predominantly yielded large, blocky crystals of sodium sulfate decahydrate (Na 2 SO 4 .10H 2 O). Successful synthesis of pure Kogarkoite was achieved exclusively in specific NaOH-free compositional windows, where the precipitate manifested as fine, opaque granular aggregates. Ion chromatography (IC) analysis confirmed phase purity through the simultaneous stoichiometric depletion of both fluoride and sulfate from the supernatant. This successful synthesis establishes a reproducible route to generate bulk Kogarkoite, enabling the subsequent phase of quantitative dissolution testing using inhibited water to optimize sludge-batch assembly.

Sarker, Md Sharif [Florida International Univ. (FI↗

Soluble Synthetic Analogs of Malaria Pigment: Structure of Mesohematin Anhydride [FeIII(MP-IX)]2 and Solution Interaction with Chloroquine

Changing the vinyl groups of hematin anhydride to either ethyl or hydrogen groups results in increased solubility (Por=porphyrin). Determination of the weak binding constants of the antimalarial drug chloroquine to dimers of these hematin anhydride analogues suggests that solution-phase heme/drug interactions alone are unlikely to be the origin of the action of the drug.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of [(3,4,5‐F 3 C 6 H 2 )(4‐ n BuC 6 H 4 ) 2 C][HCB 11 Cl 11 ]: A Much More Soluble Version of the Trityl Cation with Slightly Higher Lewis Acidity

A new triarylmethyl cation (*Tr + ), designed to closely mimic Ph 3 C + in reactivity, has been prepared as a [HCB 11 Cl 11 ] − salt. *Tr + very slightly exceeds the Lewis acidity of Ph 3 C + in chloride and hydride transfer reactions, but possesses two orders of magnitude higher solubility in organic solvents of low polarity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of nitrate on the redox chemistry and solubility of Tc(IV) in alkaline, dilute to concentrated aqueous NaCl solutions

Here, the impact of nitrate on the redox behaviour and solubility of 99 Tc(IV) was investigated in 0.1–5.0 M NaCl–NaNO 3 –NaOH solutions with 0.1 M ≤ [NO 3 – ] ≤ 1.0 M and 8.5 ≤ pH m ≤ 14.5 (with pH m = –log [H + ]) in the presence or absence of reducing agents (as Fe powder, Na 2 S 2 O 4 , Sn(II)). The evolution of the redox conditions as a function of time (for t ≤ 450 days) was investigated: (i) in the absence of technetium (inactive samples), (ii) in the presence of 99 Tc(IV) (added as 1–2 mg of TcO 2 ∙0.6H 2 O(am)), and (iii) in the presence of 137 Cs(I) (and absence of 99 Tc). All experiments were conducted in an Ar-glovebox (O 2 < 1 ppm) at T = (22 ± 2) °C. An improved understanding of Tc redox processes in nitrate-rich alkaline solutions is relevant to predict Tc behaviour in specific nuclear waste disposal scenarios and a topic of fundamental scientific interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Portlandite solubility and Ca2+ activity in presence of gluconate and hexitols

The current paper investigates the impact of gluconate, D-sorbitol, d-mannitol and D-galactitol on calcium speciation at high pH values by i) solubility measurements of portlandite (Ca(OH){sub 2}) and ii) potentiometric titration measurements of calcium salt solutions. Thermodynamic modelling was used to fit the chemical activities of Ca{sup 2+} and OH{sup −} ions and thus to determine the strength and kind of the different Ca-organic-hydroxide complexes. The strength of complex formation with Ca{sup 2+} decreases in the order gluconate ≫ sorbitol > mannitol > galactitol, which follows the same order as sorption on portlandite. Heteropolynuclear gluconate complexes with calcium and hydroxide dominate the Ca-speciation in the presence of portlandite, while for sorbitol ternary CaSorbOH{sup +} complexes were dominant under alkaline conditions. We expect that these results will help in better understanding the influence of gluconate and hexitols on the hydration of alite and Portland cement.

36 MATERIALS SCIENCE↗