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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Issue Resolution During the Development of the Performance Assessment for the Savannah River Site Saltstone Disposal Facility - 20125

In 2019, Savannah River Remediation developed a revision to the performance assessment (PA) on behalf of the U.S. Department of Energy (DOE) Savannah River Operations Office (SR) for the near-surface disposal of low-level waste at the Savannah River Site (SRS) Saltstone Disposal Facility (SDF). Soluble waste from SRS Tank Farms undergoes salt processing to remove cesium and other high-activity constituents. The low-activity decontaminated salt solution (DSS) is then immobilized by mixing it into a cementitious waste form known as saltstone. After mixing, the saltstone is poured into leak-tight concrete vaults, known as saltstone disposal units (SDUs), where the waste form cures. By the time of facility closure, the SDF is expected to consist of 15 SDUs with a combined capacity of 1.06 E+09 L (280 Mgal) of cured saltstone. The facility operates under a Disposal Authorization Statement from DOE and a permit from the South Carolina Department of Health and Environmental Control (SCDHEC). Since the start of operations in 1990, the SDF has received almost 6.7 E+07 L (18 Mgal) of DSS, resulting in the safe disposal of 2.7 E+16 Bq (7.3 E+05 Ci) of activity. Due to the radioactive decay of short-lived contaminants, the total remaining activity in the disposed waste is estimated to be approximately 1.4 E+16 Bq (3.9 E+05 Ci), as of September 2018. The Disposal Authorization Statement requires a demonstration that the system of engineered and natural features of the disposal facility will limit releases from the facility and be protective of human health and the environment for at least the next 1,000 years. The long-term performance of the facility was evaluated under the requirements of the DoE's Radioactive Waste Management Manual (US DOE Manual 435.1-1). Simulations were performed to demonstrate that the disposal facility would meet performance objectives specified in the manual. The evaluation was based on numerical models that simulate the releases of contaminants from the saltstone waste form. Contaminants were transported through groundwater and air pathways to points of assessment to evaluate compliance (i.e., 100 m from the SDUs). In addition, the potential consequences of an inadvertent human intrusion (IHI) were also evaluated. A number of issues were overcome during the development of these simulations. These issues were identified as part of internal technical reviews. Simulations are developed by people and people make mistakes, so the internal technical review process is a vital step in PA development. Specific examples of resolved issues include a unit-conversion error, an inappropriate definition for a model boundary condition, a model time-stepping issue, and an error in the calculation for the buildup of contaminants in soil. Actions taken to address these issues resulted in an improved product with a better supported technical basis and more defensible results. The identification and correction of these issues are discussed. By understanding these issues, model developers and technical reviewers working on PAs in the future may avoid repeating these types of mistakes. Transparency with respect to these mistakes builds trust between waste management sites, regulators, and stakeholders. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Wash Penalty Factors: Insight into the Effects of Water Wash Down of Building Materials for Radionuclide/Nuclear (Rn) Decontamination - 20153

The release of radiological material to the urban environment can have a devastating socio-economic impact. In an urban release scenario, areas around the dispersal epicenter and any areas contaminated via atmospheric deposition may require extensive decontamination. Most recently, our group reported the decontamination efficacy of pressurized water washing of common porous building materials, and compared the penetration depth of the contaminations before and after exposure to pressurized tap water. Here, we continue evaluation of the decontamination efficacy of wash solutions based on potassium (K{sup +}) salt for cesium (Cs), strontium (Sr), and europium (Eu) contaminations on common building surfaces. The surfaces included: the cement used in concrete, the aggregate used in concrete, intact concrete, roadway asphalt, asphalt shingles, and latex paint. We deposited solutions of {sup 137}Cs, {sup 85}Sr, and {sup 152}Eu onto numerous common building materials and exposed these materials to a static bath or low-pressure flow of tap water, 0.1 M potassium chloride (KCl), and 0.5 M KCl. The decontamination efficacy and the depth profile for residual contamination were measured to determine the conditions under which applying a wash solution has benefit compared to physically removing the surface material. To aid in these analyses, we introduced a 'wash penalty factor' to quantify the degree to which contamination migrated into the bulk material by the action of the wash method. On asphalt, 70-80% of the radionuclides were found to be within 0.02 mm of the surface. Cs{sup +} bonded to negative charge sites on the surface of the mineral aggregate (used in concrete) so decontamination was improved by ion exchange with K{sup +}. Sr{sup 2+} is soluble and removed by water, while not bonding to aggregate or demonstrating solubility in the liquid asphalt. Eu{sup 3+} is precipitated and not removed in gentle wash but displays mobility within the pore space that suggests its presence as a colloid. Concrete is more porous than asphalt, and 80% of the radionuclides were within 0.2 mm of the surface for {sup 137}Cs and {sup 152}Eu and 50- 80% for {sup 85}Sr. On concrete, Cs{sup +} bonds similarly to asphalt. Sr{sup 2+} bonds to the cement or precipitates from the alkaline pore water. Eu{sup 3+} sorbs to the cement and then precipitates. In brick, the results for Cs{sup +} and Sr{sup 2+} suggested that diffusion of ions from deeper in the coupon was important. Eu{sup 3+} is removed poorly due to precipitation. We will explain and report example wash penalty factors that vary from 0 to > 1 for the various methods and the implications for deciding when to implement wash down methods. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS2019

Perchlorate on Mars - Overview and Implications

Perchlorate was first detected on Mars by the Wet Chemistry Laboratory (WCL) instrument on the Phoenix lander at a concentration of ~0.5 wt% in northern plains soils. Since that initial detection, perchlorate (and likely chlorate) have been detected on Mars by both surface and orbital instruments. Perchlorate (ClO4-) is an oxidized chlorine compound and salts of perchlorate are kinetically stable (though very reactive at high temperature), very soluble, deliquescent, and have low eutectic temperature (which decreases the temperature for stable liquids on Mars). Chlorate (ClO3-) salts are similar, though they are less kinetically stable than perchlorates. Because many of the analytical signatures of perchlorate and chlorate are similar to the instruments we have used on Mars, we cannot always determine which species is present, so we will use the more generic term “oxychlorine” when referring to perchlorate and/or chlorate.

Archer, P. D.↗
DOE OSTI2021

Interplay of folded domains and the disordered low-complexity domain in mediating hnRNPA1 phase separation

Abstract Liquid–liquid phase separation underlies the membrane-less compartmentalization of cells. Intrinsically disordered low-complexity domains (LCDs) often mediate phase separation, but how their phase behavior is modulated by folded domains is incompletely understood. Here, we interrogate the interplay between folded and disordered domains of the RNA-binding protein hnRNPA1. The LCD of hnRNPA1 is sufficient for mediating phase separation in vitro. However, we show that the folded RRM domains and a folded solubility-tag modify the phase behavior, even in the absence of RNA. Notably, the presence of the folded domains reverses the salt dependence of the driving force for phase separation relative to the LCD alone. Small-angle X-ray scattering experiments and coarse-grained MD simulations show that the LCD interacts transiently with the RRMs and/or the solubility-tag in a salt-sensitive manner, providing a mechanistic explanation for the observed salt-dependent phase separation. These data point to two effects from the folded domains: (i) electrostatically-mediated interactions that compact hnRNPA1 and contribute to phase separation and (ii) increased solubility at higher ionic strengths mediated by the folded domains. The interplay between disordered and folded domains can modify the dependence of phase behavior on solution conditions and can obscure signatures of physicochemical interactions underlying phase separation.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1984

High-Flow Asymmetric Reverse-Osmosis Membranes

Water-soluble polymer membrane insolubilized by transition-metal salt. Thin layer of lower permeability material joined with thicker layer of highpermeability material. Two layers chemically identical or chemically distinct. They differ in density, compactness or other respects. Used to purify or desalinate seawater, brackish water, or industrial or domestic wastewater.

Katz, M. C.↗
NASA NTRS1993

Mars aqueous chemistry experiment

The Mars Aqueous Chemistry Experiment (MACE) is designed to conduct a variety of measurements on regolith samples, encompassing mineral phase analyses, chemical interactions with H2O, and physical properties determinations. From these data, much can be learned or inferred regarding the past weathering environment, the contemporaneous soil micro-environments, and the general chemical and physical state of the Martian regolith. By analyzing both soil and duricrust samples, the nature of the latter may become more apparent. Sites may be characterized for comparative purposes and criteria could be set for selection of high priority materials on future sample return missions. Progress for the first year MACE PIDDP is reported in two major areas of effort: (1) fluids handling concepts, definition, and breadboard fabrication and (2) aqueous chemistry ion sensing technology and test facility integration. A fluids handling breadboard was designed, fabricated, and tested at Mars ambient pressure. The breadboard allows fluid manipulation scenarios to be tested under the reduced pressure conditions expected in the Martian atmosphere in order to validate valve operations, orchestrate analysis sequences, investigate sealing integrity, and to demonstrate efficacy of the fluid handling concept. Additional fluid manipulation concepts have also been developed based on updated MESUR spacecraft definition. The Mars Aqueous Chemistry Experiment Ion Selective Electrode (ISE) facility was designed as a test bed to develop a multifunction interface for measurements of chemical ion concentrations in aqueous solution. The interface allows acquisition of real time data concerning the kinetics and heats of salt dissolution, and transient response to calibration and solubility events. An array of ion selective electrodes has been interfaced and preliminary calibration studies performed.

Clark, Benton C.↗
NASA NTRS1994

Oligonucleotides as probes for studying polymerization reactions in dilute aqueous solution

We have prepared a [32P]-labled oligonucleotide probe carrying a free primary amine at its 3'-terminus. This probe is used to initiate polymerization of aziridine (ethyleneimine) in aqueous solution. The nature of the oligomeric products and the kinetics of their formation are then monitored by gel electrophoresis. Our results are generally consistent with those obtained using conventional techniques. We have also investigated the effect of polyanionic templates on the rate of oligomerization of aziridine. We find that water-soluble polyanions generally accelerate the polymerization. The sodium salt of polymethacrylic acid is the most effective of the templates that we studied. The methods introduced in this paper should be applicable to a variety of polymerization reactions in aqueous solution. They should greatly simplify the screening of potentially prebiotic polymerization reactions.

NASA Discipline Exobiology↗
DOE OSTI2022

Thermostable haloarchaeal inorganic pyrophosphatase

The invention pertains to a PPA from a microorganism belonging to the family Halobacteriaceae (HPPA), for example, a PPA from Haloferax volcanii. The HPPA provided by the invention is soluble, thermostable and active at high concentrations of salt and/or organic solvent. An embodiment of the invention provides a method of increasing the rate of a reaction by adding an HPPA to the reaction mixture, wherein the reaction produces PPi, for example, an enzymatic reaction, and wherein the reaction is carried out at moderately high temperature and/or low water activity. Further embodiments of the invention provide an assay to detect the PPi released during a reaction which produces PPi by adding an HPPA to convert the PPi in to Pi and measuring the resultant Pi. The invention further pertains to an assay to monitor a reaction which produces PPi in the presence or the absence of an HPPA.

Maupin-Furlow, Julie A.↗
NASA NTRS1976

Effects of subfornical organ extracts on salt-water balance in the rat

The subfornical organ (SFO) is a circumventricular structure located at the junction of the lamina terminalis and the tela choroidea of the third cerebral ventricle. SFO is histologically regarded as a neurosecretory structure, although the physiological effects or biochemical nature of such secretions are not yet ascertained. Results are presented for an experimental study designed to determine whether SFO extracts alter parameters associated with salt-water balance in the rat. The data obtained support the conclusion that SFO contains some water-soluble substance(s), easily released by incubation, dialyzable and heat stable, which influences the salt-water balance after injection into ventricular cerebrospinal fluid. Whether other brain tissues or plasma contains the same or similar material is not yet convincingly established. The observation that one or more active constituents are easily released from SFO upon incubation in potassium-enriched medium may be of value.

Summy-Long, J. Y.↗
DOE OSTI2021

Association‐based activity coefficient model for electrolyte solutions

Abstract This work presents an association‐based activity coefficient model that explicitly considers the solution nonideality due to associations among ions and solvent species. Built upon the electrolyte nonrandom two‐liquid (eNRTL) model, the model greatly improves the accuracy of eNRTL model for strongly associating electrolyte solutions due to presence of ionic species with high surface charge density. The model successfully correlates mean ionic activity coefficients of 46 aqueous single‐salt systems from 10 cations and 5 anions at 298.15 K up to their solubility limits. With the ion‐specific association parameters identified, the model accurately predicts activity and osmotic coefficients for aqueous mixed‐salt systems at 298.15 K. The temperature dependence of the model results has also been examined at 273–373 K. With superior accuracy over a wide range of concentration and temperature, the model represents a major advancement over eNRTL model and has a great potential to be a next‐generation model for electrolyte solutions.

Lin, Yu‐Jeng↗
DOE OSTI2021

Mechanically robust hydrophobized double network hydrogels and their fundamental salt transport properties

Abstract Water swollen polymer networks are attractive for applications ranging from tissue regeneration to water purification. For water purification, charged polymers provide excellent ion separation properties. However, many ion exchange membranes (IEMs) are brittle, necessitating the use of thick support materials that ultimately decrease throughput. To this end, novel double network hydrogels (DNHs) with variable water content are prepared and characterized in terms of mechanical and ion transport properties to evaluate their potential utility as tough membrane materials. The first network contains fixed anionic charges, while the other is comprised of a copolymer with varied ratios of hydrophobic ethyl acrylate (EA) and hydrophilic dimethyl acrylamide (DMA) repeat units. Characterization of freestanding DNH films reveals a reduction in water content from 88 to 53 wt% and a simultaneous increase in ultimate stress and strain by ~3.5× and ~4.5×, respectively, for 95%/5% EA/DMA, relative to 100% DMA. Fundamental salt transport properties relevant to water purification, including permeability, solubility, and diffusivity, are measured and systematically compared with conventional membrane materials to inform the development of DNHs for membrane applications. The ability to simultaneously reduce water content and increase mechanical integrity highlights the potential of DNHs as a synthetic platform for future membrane applications.

Allen, Marshall J.↗
DOE OSTI2021

In-situ anodic precipitation process for highly efficient separation of aluminum alloys

Electrorefining process has been widely used to separate and purify metals, but it is limited by deposition potential of the metal itself. Here we report in-situ anodic precipitation (IAP), a modified electrorefining process, to purify aluminium from contaminants that are more reactive. During IAP, the target metals that are more cathodic than aluminium are oxidized at the anode and forced to precipitate out in a low oxidation state. This strategy is fundamentally based on different solubilities of target metal chlorides in the NaAlCl4 molten salt rather than deposition potential of metals. The results suggest that IAP is able to efficiently and simply separate components of aluminum alloys with fast kinetics and high recovery yields, and it is also a valuable synthetic approach for metal chlorides in low oxidation states.

36 MATERIALS SCIENCE↗
NASA NTRS1992

Coupling plant growth and waste recycling systems in a controlled life support system (CELSS)

The development of bioregenerative systems as part of the Controlled Ecological Life Support System (CELSS) program depends, in large part, on the ability to recycle inorganic nutrients, contained in waste material, into plant growth systems. One significant waste (resource) stream is inedible plant material. This research compared wheat growth in hydroponic solutions based on inorganic salts (modified Hoagland's) with solutions based on the soluble fraction of inedible wheat biomass (leachate). Recycled nutrients in leachate solutions provided the majority of mineral nutrients for plant growth, although additions of inorganic nutrients to leachate solutions were necessary. Results indicate that plant growth and waste recyling systems can be effectively coupled within CELSS based on equivalent wheat yield in leachate and Hoagland solutions, and the rapid mineralization of waste organic material in the hydroponic systems. Selective enrichment for microbial communities able to mineralize organic material within the leachate was necessary to prevent accumulation of dissolved organic matter in leachate-based solutions. Extensive analysis of microbial abundance, growth, and activity in the hydroponic systems indicated that addition of soluble organic material from plants does not cause excessive microbial growth or 'biofouling', and helped define the microbially-mediated flux of carbon in hydroponic solutions.

Garland, Jay L.↗
NASA NTRS2000

The Effects of Thermal History on Nucleation of Tetragonal Lysozyme Crystals, or Hot Protein and Cold Nucleation

Chicken egg white lysozyme has a well characterized thermally driven phase transition. Between pH 4.2 and 5.2, the transition temperature, as defined by the point where the tetragonal and orthorhombic solubilities are equal, is a function of the pH, salt (precipitant) type and concentration, and most likely of the buffer concentration as well. This phase transition can be carried out with protein solution alone, prior to addition of precipitant solution. Warming a lysozyme solution above the phase transition point, then cooling it back below this point, has been shown to affect the subsequent nucleation rate, as determined by the numbers and size of crystals formed, but not the growth rate for the tetragonal crystal form . We have now measured the kinetics of this process and investigated its reversibility. The transition effects are progressive with temperature, having a half time of about 1 hour at 37C at pH 4.8. After holding a lysozyme solution at 37C (prior to addition of precipitant) for 16 hours, then cooling it back to 4C no return to the pre-warmed nucleation kinetics are observed after at least 4 weeks. Orthorhombic lysozyme crystals apparently do not undergo the flow-induced growth cessation of tetragonal lysozyme crystals. Putting the protein in the orthorhombic form does not affect the averaged face growth kinetics, only nucleation, for tetragonal crystals. This differential behaviour may be exploited to elucidate how and where flow affects the lysozyme crystal growth process. The presentation will focus on the results of these and ongoing studies in this area.

Burke, Michael↗
NASA NTRS2000

Does Warming a Lysozyme Solution Cook Ones Data?

Chicken egg white lysozyme has a well characterized thermally driven phase transition. Between pH 4.0 and 5.2, the transition temperature, as defined by the point where the tetragonal and orthorhombic solubility are equal, is a function of the pH, salt (precipitant) type and concentration, and most likely of the buffer concentration as well. This phase transition can be carried out with protein solution alone, prior to the initiation of the crystallization process. We have now measured the kinetics of this process and investigated its reversibility. An aliquot of a stock protein solution is held at a given temperature, and at periodic intervals used to set up batch crystallization experiments. The batch solutions were incubated at 20 C until macroscopic crystals were obtained, at which point the number of crystals in each well were counted. The transition effects increased with temperature, slowly falling off at 30 C with a half time (time to approx. 1/2 the t = 0 number of crystals) of approx. 5 hours, and an estimated half time of approx. 0.5 hours at 43 C. Further, the process was not reversible by simple cooling. After holding a lysozyme solution at 37 C (prior to addition of precipitant) for 16 hours, then cooling and holding it at 4 C, no return to the pre-warmed nucleation kinetics are observed after at least 4 weeks. Thus every thermal excursion above the phase transition point results in a further decrease in the nucleation rate of that solution, the extent being a function of the time and temperature. Orthorhombic lysozyme crystals apparently do not undergo the flow-induced growth cessation of tetragonal lysozyme crystals. We have previously shown that putting the protein in the orthorhombic form does not affect the averaged face growth kinetics, only nucleation, for tetragonal crystals. We may be able to use this differential behavior to elucidate how flow affects tile lysozyme crystal growth process.

Pusey, Marc↗
NASA NTRS2006

Fossils of Prokaryotic Microorganisms in the Orgueil Meteorite

The Orgueil CII meteorite, which fell in southern France on the evening of May 14, 1864, has been one of the most extensively studied of all known carbonaceous meteorites. Field Emission Scanning Electron Microscopy (FESEM) studies of freshly fractured interior surfaces of the Orgueil meteorite have resulted in the detection of the fossilized remains of a large and diverse population of filamentous prokaryotic microorganisms. The taphonomy and the diverse modes of the preservation of these remains ,are diverse. Some of the remains exhibit carbonization of a hollow sheath and in other cases the remains are permineralized with water-soluble evaporite minerals, such as magnesium sulfate or ammonium salts. After the sample is fractured and the interior surfaces are exposed to the atmospheric moisture, some of these friable remains have been observed to exhibit significant alterations in appearance with time. Images are presented to document the changes that have been observed in some forms within the past two years. Images and EDS spectral data will also be presented to document the studies carried out on abiotic forms to search for possible nonbiological interpretations of the indigenous filamentous microstructures that have been found in the Orgueil meteorite. Images and EDS data will be presented showing the size, size range, morphology and chemical compositions of abiotic microstructures found in native crystalline and fibrous Epsomites from Poison Lake, Washington, USA and Catalayud, Zaragoza, Aragon, Spain. Many of these embedded forms are consistent in size and microstructure with cyanobacteria morphotypes. Some of the forms are exhibit known characteristics differentiation of cells, and reproductive structures of filamentous trichomic prokaryotes (bacteria and cyanobacteria) and the degraded remains of microfibrils associated with sheaths of cyanobacteria. In this paper, recently obtained comparative images and EDS data will be presented for the mineralized remains found in the Orgueil meteorite and these forms will be compared with known cyanobacteria of the family Oscillatoriaceae. Many of the indigenous filamentous microstructures found in Orgueil filaments are dramatically different from the abiotic microstructures found in the fibrous epsomites and these forms are interpreted as the molds, casts and the well preserved permineralized remains (microfossils) of filamentous prokaryotes that are embedded in and indigenous to the matrix of the Orgueil CI1 carbonaceous meteorite.

Hoover, Richard B.↗
DOE OSTI2021

Selection of Glasses to Confirm the 0.65 Weight Percent Sulfate Solubility Limit for Sludge Batch 10

In preparation for Sludge Batch 10 (SB10) processing, projections of sulfate (SO 4 2- ) in glass at 36% waste loading (WL) were calculated in May 2020 for Tank 40 blend projections representing 0.7M and 0.85M Na wash endpoints. The projected SO 4 2- ) concentrations for either sludge-only (SO) or coupled processing with the Salt Waste Processing Facility (SWPF) were either near or exceeded the current Sludge Batch 9 (SB9) limit of 0.65 weight percent (wt.%). Four nominal glass compositions were selected based on SO and coupled processing for the 0.85M Na wash endpoint Tank 40 blend projection to conduct an initial evaluation of the SB10 sulfate solubility behavior. A sulfate salt phase was absent from each of the prepared glasses, which provided preliminary results that supported the 0.65 wt.% SO 4 2- ) limit for SB10.

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

Sulfur Solutions: Advancing High Voltage and High Energy Lithium Batteries with Organosulfur Electrolytes

Achieving energy densities exceeding 350 Wh kg -1 while operating at elevated voltages (>4.5 V vs Li/Li + ) is attainable through judicious selection of electrochemical pairs at the cathode and anode. However, current state-of-the-art electrolytes exhibit limited stability when exposed to systems operating at or above 4.3 V. This limitation contributes to the degradation of electrode materials and raises critical safety concerns, impeding the commercialization of such systems. Consequently, there has been a notable surge in research efforts aimed at developing innovative electrolyte compositions capable of supporting high-voltage lithium-ion batteries (LIBs). A substantial portion of this research has focused on the family of organosulfur molecules, which possess high oxidative stability. Organosulfur salts also facilitate the formation of dense, ionically conductive solid electrolyte interfaces (SEI) and demonstrate excellent solubility. This article provides a comprehensive overview of the field of organosulfur electrolyte components for their applications in energy storage, encompassing solvents, alternative conducting salts, and additives. It emphasizes the idea that the deliberate design of electrolyte compositions is instrumental in controlling electrode passivation, with organosulfur-based structures historically proving advantageous in every aspect of the electrolyte. Crucially, it should be noted that many of these components are commercially available, holding significant implications for industrial applications.

25 ENERGY STORAGE↗