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At least 1,081 records · Page 60

Is Water Necessary for Life?

The universality of water as the solvent for life is usually justified by its role in supporting the rich organic chemistry. It has been pointed out, however, that even richer synthetic chemistry is possible in other organic solvents. Does it mean that water is not necessary for life? Here, other, essential criteria for solvent for life that have not been sufficiently considered are discussed. In biological systems, complex molecules are not only constantly synthesized but also degraded. Solvent-mediated degradation is essential for regulating cell content, preventing overcrowding and allowing for recycling organic material. Achieving a balance between synthetic and degradative processes is facile in water, but not in many other organic liquids. Thus, the so-called “water paradox” according to which water is both necessary to life and toxic to biopolymer synthesis might not be paradoxical at all. The machinery of life is based on non-covalent interactions that do not involve making or breaking chemical bonds. Their strength needs to be properly tuned. If they are too weak, there might be undesired response to natural fluctuations of physical or chemical parameters. If they are too strong, the kinetics and energetics of cellular processes could adversely influenced. The solvent must allow for balancing these interactions, which provides strong, universal constraints on the medium for life. Water influences non-covalent interactions mainly by two mechanisms. First, it reduces strong, electrostatic interactions between molecules, chemical groups or atoms carrying electric charge or dipole. Second, it induces the hydrophobic effect, the tendency to remove non-polar (hydrophobic) molecules and groups from direct contact with aqueous solution and, instead, interact with each other. In living systems, the hydrophobic effect is largely responsible for self-organization of molecules to more complex structures, such as aggregation of lipid molecules to form biological membranes and protein folding. Water exists as stable liquid in a large temperature range, and the hydrophobic effects are a consequence of the temperature insensitivity of essential properties of its liquid state. In summary, water accomplishes an amazing feat – it reduces strong interactions between dissolved species and simultaneously increases the strength of weak interactions, bringing all of them to the right range. Once we consider not only synthetic capabilities but also other required traits of the solvent for life, no viable alternative to water is currently known.

Life↗

Direct Analyses of Aqueous Fluids from C-Class Asteroid 162173 Ryugu

Imaging using X-ray absorption contrast by synchrotron nano-computed tomography (47.4 nm/voxel, 7keV) of a Ryugu pyrrhotite crystal revealed probable fluid inclusions. The inclusions were completely encapsuled in pyrrhotite, suggesting the fluids were trapped in the early stages of crystal growth, and filled with low-Z material. We performed Time-of Flight-Secondary Ion Mass Spectrometry (TOF-SIMS) depth profiling and high-resolution mapping at -120°C to exposure and measure the composition of the trapped fluids in a frozen state. These measurements revealed that the ancient, trapped fluids on Ryugu’s parent asteroid were saline aqueous solutions containing H2O, CO2, sulfur species, and nitrogen- and chlorine-bearing organic compounds identified by representative secondary ion species including O(-), OH(-), CO(-), S(-), Cl(-), C2(-), C2H(-), and CN(-). The inferred presence of CO2 indicates formation of the sulfides, and by implication the Ryugu parent body, beyond the H2O and CO2 snow lines of the early solar system, i.e. > 3-4 au from the Sun.

M Zolensky↗

Testing and Application of Commercial Thermodynamics Software for Solid-Gas Equilibria in Planetary Science Applications

The ability to calculate chemical equilibria from thermochemical constants (e.g., H, S, Cp) or other experimental data is a tool widely employed by scientists. However, phase equilibria for planetary science problems is limited by easy access to libraries of thermochemical data, as well as the software to invert that data. Many academic software packages are focused on specific types of problems (e.g., aqueous solutions or melting and crystallization of magmas). This focus makes them excellent tools for specific uses, but poorer tools for other scenarios, especially those involving elements or chemical species that are less well-studied in that specific scientific field (e.g. NaCl vapor). Amongst the more general thermodynamic software tools, there are closed academic software packages, open-source options, as well as commercial software. We have explored the extent to which commercial chemistry/chemical engineering software may be able to satisfy the need for thermochemical modeling packages that can accommodate the diverse species and conditions of planetary science problems. Here we compare the output of software package HSC Chemistry™ (Metso Outotec) to published vapor-solid phase diagrams for a variety of major and minor elements. HSC Chemistry™ has been used in several recent geochemical studies of terrestrial volcanic systems [2- 4]. However, it has not to our knowledge been benchmarked against peer-reviewed model results for the conditions and compositions relevant to planetary science. We present one such comparison here, the low- pressure environment of the solar nebula, using literature data. In short, we find excellent agreement between HSC Chemistry™ and the well-regarded academic software package CONDOR. These preliminary results suggest that at least some commercial software packages are capable of robust thermochemical calculations for planetary science.

planetary science↗

A Brief Review of Chaotropic vs. Kosmotropic Salts on the Degree of Saturation of Membrane Fatty Acids: Implications for Preservation of Environmental Biomarkers

Water activity is well known to have a significant impact on habitability, due to the presence of salts. However, salt composition is also important for habitability, as it can impact microbial activity and biomolecular interactions since certain salts are known to disrupt hydrogen bonding. Chaotropic agents disrupt hydrogen bonding in aqueous solutions leading to increased entropy (chaos) whereas kosmotropic agents are compounds that promote hydrogen bonding (order). The Hofmeister series (Fig. 1) shows the ordering of ions in terms of their ability to stabilize and induce precipitation or aggregation of proteins.

M B Wilhelm↗

Battery cell with safety layer

A battery cell comprising a composite water-responsive safety layer and/or composite water- and pH-responsive safety layer to protect against tissue damage and/or electrolysis, when the battery cell is exposed to aqueous solution or tissue, is provided. The composite water-responsive safety layer and/or composite water- and pH-responsive safety layer is adapted to change from a non-electronically conducting state to an electronically conducting state.

25 ENERGY STORAGE↗

Battery cell with safety layer

A battery cell comprising a composite water-responsive safety layer and/or composite water- and pH-responsive safety layer to protect against tissue damage and/or electrolysis, when the battery cell is exposed to aqueous solution or tissue, is provided. The composite water-responsive safety layer and/or composite water- and pH-responsive safety layer is adapted to change from a non-electronically conducting state to an electronically conducting state.

25 ENERGY STORAGE↗

Annulated tetra-substituted hydroquinone ether-based redox shuttle additives for lithium-ion batteries

An electrolyte for a lithium-ion electrochemical cell comprises a non-aqueous solution of a lithium salt and a redox shuttle compound, wherein the redox shuttle compound comprises —OR groups at carbons 1 and 4 of a benzene ring; a first hydrocarbon ring fused to carbons 2 and 3 of the benzene ring; and a second hydrocarbon ring fused to the carbons 5 and 6 of the benzene ring, wherein either (i) the first and second hydrocarbon rings together with the benzene ring constitute two fused benzobicyclo[2.2.2]octane ring systems sharing a common benzo core group; or (ii) the first and second hydrocarbon rings together with the benzene ring constitute two fused benzobicyclo[2.2.1]heptane ring systems sharing a common benzo core group.

25 ENERGY STORAGE↗

Enzymes and Models. In: XAFS Techniques for Catalysts, Nanomaterials, and Surfaces

Many important redox-active metalloenzymes consist of 3d transition metals in their active sites. They catalyze multi-electron reactions in aqueous solution, under ambient temperature and pressure. To understand the functionality of the catalytic sites of these enzymes, X-ray spectroscopy methods provide important information of the electronic structure of the metal of interest and its local structural information, as well as their changes during the catalysis. Studying model compounds, that mimic enzyme catalytic site structures or their functional mimics, is as critical as studying enzymes themselves, in order to interpret X-ray spectroscopic data. In this chapter, various X-ray spectroscopic methods that are useful for structural and electronic structural studies of enzymes and model compounds are described.

Yachandra, VK↗

Separating rare earth metal oxalates

A method is provided for separating and/or purifying different metal oxalates by mixing the different metal oxalates in an aqueous solution comprising oxalic acid and an organic base so that at least one metal oxalate is soluble and at least another metal oxalate is not soluble. Different rare earth metal oxalates and/or transition metal oxalates can be separated.

Prodius, Denis↗

Effect of Initial Water Saturation on The Performance of Fracturing Fluids With and Without Polyallylamine under Simulated EGS Conditions

Objectives/Scope: StimuFrac (US Patents 9,873,828 B2 and 9,447,315 B2), a CO2-reactive polymer aqueous solution [polyallylamine (PAA) 1wt% in water] combined with CO2, can be used as a less water-intensive fracturing fluid for enhanced geothermal systems (EGS). Our previous results show that in hot dry rock (HDR), PAA/CO2 fracturing fluids outperformed other fluids such as water, CO2, and CO2/water in generating large fractures with less fluid consumed. The objective of this work is to study the effect of initial water saturation of rock on the performance of StimuFrac fluid in ½ foot cubic rock samples and under representative EGS pressure/temperature conditions using cyclic and constant flow rate injection strategies. The fracturing results are compared with results using different fracturing fluids in terms of controlling fracture propagation rates, fracture hydraulic conductivity, breakdown pressures and volumes of fluids required. Methods/Procedures/Process: In all tests, water was initially injected into the rock to increase the water saturation before the fracturing processes to simulate actual geothermal reservoir conditions. For the cyclic injection, one complete cycle consisted of (1) a PAA slug (or water slug) injection followed by (2) CO2 injection to initiate the fracture. In the second step of the first cycle, the pressure of CO2 is increased until a maximum pressure is reached (fracture is initiated at this moment), and then the injection of CO2 is allowed for another 30 seconds to propagate the fracture. Then, the two-step cycle of PAA followed by CO2 injection (up to 2-4 mL/min) was continued. For the constant flow rate injection strategies, the initial water saturation was increased by injecting water at 1000 psi and 200°C for three days. After that, an initial slug of water, CO2, or PAA was injected and then fracturing was initiated and propagated by injecting CO2 at a constant flow rate. Applications/Significance/Novelty: The results of this study suggest that water saturation, especially near the wellbore region, will significantly affect the fracturing fluid transmission into the rock porous media by changing the relative permeability of CO2 or water, thus affecting the fracture initiation and propagation. In this study, fracturing with cyclic injection or constant flow rate injection methods were performed using three different kinds of fluids systems. These fluids are water, CO2, or CO2 with PAA. Splitting the rock samples in half after fracturing reveals that the fracture propagation is significantly limited under these high water saturated conditions compared to dry initial conditions: The fractures propagate less than 1/3 length of the distance from the wellbore to rock surface, and in some cases no fracture is generated. This may be caused by the fact that leak-off is dominating the fracturing process and the injected fluid flow rate is not high enough to overcome the leak-off even under high flow rate injection conditions. Additionally, CO2 could be leaking off into the wellbore annulus and this may be making it more difficult to generate pressure gradients away from the near-wellbore region.

Jian, Guoqing↗

Battery cell with safety layer

A battery cell comprising a composite water-responsive safety layer and/or composite water- and pH-responsive safety layer to protect against tissue damage and/or electrolysis, when the battery cell is exposed to aqueous solution or tissue, is provided. The composite water-responsive safety layer and/or composite water- and pH-responsive safety layer is adapted to change from a non-electronically conducting state to an electronically conducting state.

Pozin, Michael↗

Transamericium Radiation-Induced Redox Chemistry

The actinide series boasts many unique physical and chemical features worthy of study. However, the chemical influence of their inherent radiation field is often overlooked, especially as we begin to explore the late actinides (transamericium) in more detail than ever possible before. - Absorption of ionizing radiation induces the formation of a variety of transient and steady-state radicals, ions, and molecular degradation products. Many of these radiolysis products are strongly redox active and exhibit significant reactivity with a number of actinides, e.g., neptunium and americium. Here we present results from the first-ever time-resolved picosecond pulsed electron radiolysis measurements for the reaction of the late actinides (curium and californium) with reactive transients pertinent to actinide manipulations in aqueous solution, i.e., the hydrated electron (eaq–), the hydrogen atom (H•), and hydroxyl (•OH) and nitrate (•NO3) radicals.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Nanopore device for reversible ion and molecule sensing or migration

Disclosed are methods and devices for detection of ion migration and binding, utilizing a nanopipette adapted for use in an electrochemical sensing circuit. The nanopipette may be functionalized on its interior bore with metal chelators for binding and sensing metal ions or other specific binding molecules such as boronic acid for binding and sensing glucose. Such a functionalized nanopipette is comprised in an electrical sensor that detects when the nanopipette selectively and reversibly binds ions or small molecules. Also disclosed is a nanoreactor, comprising a nanopipette, for controlling precipitation in aqueous solutions by voltage-directed ion migration, wherein ions may be directed out of the interior bore by a repulsing charge in the bore.

47 OTHER INSTRUMENTATION↗

Calcined Polyethyleneimine Coated Optical Fibers for Distributed pH Monitoring at High Pressures and Temperatures

In the oil and gas, CO2 sequestration, H2 subsurface storage, and geothermal energy sectors, subsurface pH measurements are critical for monitoring the geochemical conditions and estimating potential corrosion rates of wellbore systems. Real-time pH measurements in these conditions are vital for detecting and predicting corrosion deterioration of wellbore components that may jeopardize the safety and continued operation of wellbore systems. Building off of earlier TiO2 based pH sensors and the known pH sensitivity of amine-based polymers, a coating based on the secondary amine polymer polyethyleneimine (PEI) was developed. The sensor coating was treated with a high temperature (500 °C) calcination procedure in air to convert it into a more stable oxidized coating capable of withstanding hot aqueous solutions without dissolving while retaining linear pH sensitivity from pH values between 2 and 11. The sensor performance was measured using optical transmission measurements in solutions of various pHs and using optical backscatter reflectometry for distributed pH sensing demonstration in wellbore-relevant pressures (up to 1000 psi) and temperatures (80 °C). A calibration curve with strong differentiation between acidic and alkaline pH was developed for both transmission-based and distributed pH measurements, using fixed wavelength transmission and integrated linear amplitude of backscattered light for distributed measurements.

Shumski, Alexander↗

Lost and Found Opportunities Around the Chlorine Worth Study

Los Alamos National Laboratory performed a series of critical experiments in 2021 to examine the worth of chlorine in plutonium-fueled systems. This series of experiments has been dubbed the “Chlorine Worth Study,” and the evaluation of the experiments was presented to the International Criticality Safety Benchmark Evaluation Project (ICSBEP) Technical Review Group in April, 2023. The primary purpose of these experiments was to enable validation of aqueous solutions crediting neutron absorption in 35 Cl. An external, independent view of the events leading up to the design and execution of these experiments indicates a missed opportunity to leverage sensitivity/uncertainty (S/U) analysis to assert validation without the experiments by taking an additional margin for the lack of direct validation of chlorine. On the other hand, the execution of these experiments also presents a rare opportunity to examine the efficacy of the S/U approach and extract useful information about the evaluated chlorine covariance data. TSUNAMI-1D models of representative application solutions were created and used to generate sensitivity data. Varying plutonium and chlorine concentrations were considered to examine the impact of these differences on the chlorine sensitivities and uncertainties. The data-induced uncertainty in k eff resulting from chlorine was calculated directly from uncertainty information calculated in the TSUNAMI-1D sequence. In all cases, this uncertainty was less than 0.1 %Δk. This result could potentially be used to justify a reactivity margin to account for the validation gap related to chlorine in the validation set. On the other hand, given that the experiments were performed, the community should endeavor to extract as much value from them and their results as possible. The results can be used to examine the actual bias associated with chlorine in these systems once the evaluations have been released. These data can be compared with the data-induced uncertainty margin discussed above to test the sufficiency of the validation gap penalty. This result will provide an indication of the performance of the chlorine covariance data specifically and the S/U validation approach generally. More advanced S/U techniques may also be employed to determine reactivity sensitivities associated with the chlorine in the experiments, potentially generating a more robust test of the chlorine covariance data.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Evaluation of the Sum-of-Fractions Methodology for Water and Polyethylene Moderated Systems

Sum-of-Fractions is a method intended to assure a subcritical margin for aqueous solutions and slurries of fissionable isotopes. The method indicates that a system is subcritical if the sum of the ratios of the mass of each isotope in a mixture to its individual minimum subcritical mass limit is less than or equal to one. The basis of the Sum-of Fractions has historically been derived from allowances given in ANSI/ANS-8.15-1981. However, the allowance was removed in ANSI/ANS-8.15-2014 due to a lack of technical basis. A methodology was developed to assess the validity of using the Sum-of-Fractions for water or polyethylene moderated systems for the following nuclides: 232 U, 233 U, 234 U, 235 U, 237 Np, 236 Pu, 238 Pu, 239 Pu, 240 Pu, 241 Pu, 242 Pu, 241 Am, 242 mAm, 243 Am, 242 Cm, 243 Cm, 244 Cm, 245 Cm, 246 Cm, 247 Cm, 249 Cf, and 251 Cf. The methodology uses available benchmark data for mixtures of 233 U, 235 U, and 239 Pu to establish the calculational margin, and a mass limit reduction to establish the margin of subcriticality. Water or polyethylene moderated and reflected mixtures containing the nuclides are evaluated with SCALE 6.2.4. Including the calculational margin, subcritical mass limits for each nuclide were computed for optimally water or polyethylene moderated and fully reflected systems. These masses were used to create nuclide mixtures in which the sum of the mass to subcritical mass limit ratios is one. The various nuclide mixtures were modeled over a range of moderation and demonstrate the k eff does not exceed the calculational margin. For additional assurance of subcriticality, a significant mass reduction is applied to each computed minimum critical mass of the nuclides without adequate benchmark data consistent with the method in ANSI/ANS-8.15-2014.

07 ISOTOPE AND RADIATION SOURCES↗

A Molten Salt Aerosol Spectroscopy Approach to Online Process Monitoring in Molten Salt Reactors

Recent research and development in molten salt reactors (MSRs) has led to many advanced reactor designs, many of which have demonstrations planned in the next decade. However, a significant challenge that must be overcome before liquid fueled MSRs become viable globally is nuclear material accountancy (NMA) and safeguards. Liquid-fueled MSRs are problematic to safeguards because the nuclear material is in the bulk phase, inventories are constantly changing, and there are potentially many outlet pathways that must be monitored, especially in designs with online chemical processing. At the Idaho National Laboratory, we have developed a process monitoring tool to circulate molten salt through a nebulizer and optical cell, where laser-induced breakdown spectroscopy (LIBS) and ultraviolet-visible (UV-VIS) are applied to track the elemental and oxidation states of the constituents in the salt aerosol. This approach has the potential to provide information on the actinides, fission products, and corrosion in the reactor or process. Preliminary testing in aqueous praseodymium chloride (PrCl3) and neodymium chloride (NdCl3) showed good sensitivity detection limits n developed calibration curves. Additional tests and analysis or ongoing in aqueous solutions while equipment is being scaled up for high temperature molten salt testing. Results for continued testing as well as a status of the molten salt design and anticipated commissioning will be presented.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗