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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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118 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Cytoplasmic pH influences cytoplasmic calcium in MC3T3-E1 osteoblast cells

We found that the cytoplasmic concentration of calcium (Cai) of MC3T3-E1 osteoblasts was influenced by the type of pH buffer we used in the perfusing medium, suggesting that intracellular pH (pHi) might influence Cai. To study this effect, the Cai and pHi were monitored as we applied various experimental conditions known to change pHi. Exposure to NH4Cl caused a transient increase in both pHi and Cai without a change in extracellular pH (pHo). Decreasing pHo and pHi by lowering the bicarbonate concentration of the medium decreased Cai, and increasing pHi by the removal of 5% CO2 increased Cai. Clamping pHi to known values with 10 microM nigericin, a potassium proton ionophore, also influenced Cai: acid pHi lowered Cai, whereas alkaline pHi increased it. The rise in Cai appears to be very sensitive to the extracellular concentration of calcium, suggesting the existence of a pH-sensitive calcium influx mechanism. We conclude that physiologic changes in pH could modulate Cai by controlling the influx of calcium ions and could change the time course of the Cai transient associated with hormonal activation.

NASA Program Space Biology↗
NASA NTRS2018

Physical and Biological Properties of Cobalt- and Copper-Doped Calcium Phosphates as Bone Substitute Materials

Arthritis, osteoporosis, and other bone diseases and defects are common medical issues worldwide. By utilizing ceramic biomaterials as bone substitutes to treat these diseases, bone regeneration can be promoted and toxicity from the substitute material can be limited. Calcium phosphate (CaP) ceramics have become popular as bone substitutes due to their biocompatibility and similarity in composition to natural bone. The purpose of this research was to investigate the physical properties and biological responses of CaP-based bone substitutes, doped with metal ions. Some metal ions are present in natural bone in small amounts, and recent studies show they affect the biological responses of CaPs significantly. Dopants such as magnesium (Mg), strontium (Sr), silicon (Si) and iron (Fe) alter the phase composition, mechanical properties, osteogenesis and angiogenesis properties of CaPs, depending on their concentration and method of addition. In the present study, the effects of cobalt (Co) and copper (Cu) on the physical and biological properties of two main CaP materials, brushite cement (BrC) and tricalcium phosphate (TCP), have been investigated. Different concentrations of dopants in forms of oxide and/or chloride were selected and their effect on phase composition, sintering behavior, density, setting time, compressive strength and in vitro interaction with osteosarcoma and osteoblast cells were studied. Different techniques of sample preparation, challenges during cement preparation and compact sample pressing, sintering, and methods of dopant addition are discussed. The presence of Cu in tricalcium phosphate was found to increase thermal stability of the material and decrease the impact of sintering temperature on porosity. In addition, Cu caused a reduction in expression of inflammatory gene markers by human osteoblast cells and an increased expression at early time points due of osteoinductive markers.The addition of Cu and Co to brushite cement caused an increase in thermal stability of the material, and the addition of Cu caused significant increase in setting time. Small dopant amounts of Co caused decrease in setting time, but higher amounts caused an increase. In addition, Cu dopant in small amounts resulted in an increase of compressive strength. Both Cu and Co led to a decrease in expression of inflammatory gene markers by osteoblast and osteosarcoma cells respectively, and Cu also caused an increase in osteoinductive marker expression. Thus, these results indicate that Cu and Co have a positive impact on the physical, mechanical and biological properties of calcium phosphate biomaterials.

Cummings, Haley V.↗
NASA NTRS1979

Recycling plant, human and animal wastes to plant nutrients in a closed ecological system

The essential minerals for plant growth are nitrogen, phosphorous, potassium (macronutrients), calcium, magnesium, sulfur (secondary nutrients), iron, manganese, boron, copper, zinc, chlorine, sodium, and molybdenum (micronutrients). The first step in recycling wastes will undoubtedly be oxidation of carbon and hydrogen to CO2 and H2O. Transformation of minerals to plant nutrients depends upon the mode of oxidation to define the state of the nutrients. For the purpose of illustrating the type of processing required, ash and off-gas compositions of an incineration process were assumed and subsequent processing requirements were identified. Several processing schemes are described for separating out sodium chloride from the ash, leading to reformulation of a nutrient solution which should be acceptable to plants.

Meissner, H. P.↗
NASA NTRS2013

Possible Detection of Perchlorates by the Sample Analysis at Mars (SAM) Instrument: Comparison with Previous Missions

The first chemical analysis of soluble salts in the soil was carried out by the Phoenix Lander in the Martian Arctic [1]. Surprisingly, chlorine was present as magnesium or calcium perchlorate at 0.4 to 0.6 percent. Additional support for the identification of perchlorate came from the evolved gas analysis which detected the release of molecular oxygen at 350-550C [1]. When Mars-like soils from the Atacama Desert were spiked with magnesium perchlorate (1 percent) and heated using the Viking GC-MS protocol, nearly all the organics were combusted but a small amount was chlorinated, forming chloromethane and dichloromethane [2]. These chlorohydrocarbons were detected by the Viking GC-MS experiments when the Martian soil was analyzed but they were considered to be terrestrial contaminants [3]. Reinterpretation of the Viking results suggests <0.1 percent perchlorate and ppm levels of organic carbon at landing site 1 and 2 [2]. The suggestion of perchlorate in the Viking sites [2] has been challenged on the grounds that the detected compounds (CH3Cl and CH2Cl2) were carried from Earth [4]. Recently the Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory (MSL) ran four samples from an aeolian bedform named Rocknest. The samples analyzed were portioned from the fifth scoop at this location. The samples were heated to 835C at 35C/min with a He flow. The SAM QMS detected a major oxygen release (300-500C) [5], coupled with the release of chlorinated hydrocarbons (chloromethane, dichloromethane, trichloromethane, and chloromethylpropene) detected both by SAM QMS and GC-MS derived from known Earth organic contaminants in the instrument [6]. Calcium perchlorate appears to be the best candidate for evolved O2 in the Rocknest samples at this time but other Cl species (e.g., chlorates) are possible and must be evaluated. The potential detection of perchlorates in Rocknest material adds weight to the argument that both Viking Landers measured signatures of perchlorates. Even if the source of the organic carbon detected is still unknown, the chlorine source was likely Martian. Two mechanisms have been hypothesized for the formation of soil perchlorate: (1) Atmospheric oxidation of chlorine; and (2) UV photooxidation of chlorides catalyzed by mineral catalysts [7]. The presence of soil perchlorates in the Martian surface has important implications for the detection of organics [2], carbonates [8] and nitrates [9] by SAM.

Navarro-Gonzalex, Rafael↗
DOE OSTI2024

ZeroCAL: Eliminating Carbon Dioxide Emissions from Limestone’s Decomposition to Decarbonize Cement Production

Limestone (calcite, CaCO 3 ) is an abundant and cost-effective source of calcium oxide (CaO) for cement and lime production. However, the thermochemical decomposition of limestone (~800 °C, 1 bar) to produce lime (CaO) results in substantial carbon dioxide (CO 2(g) ) emissions and energy use, i.e., ~1 tonne [t] of CO 2 and ~1.4 MWh per t of CaO produced. Here, we describe a new pathway to use CaCO 3 as a Ca source to make hydrated lime (portlandite, Ca(OH) 2 ) at ambient conditions (p, T) while nearly eliminating process CO 2(g) emissions (as low as 1.5 mol. % of the CO 2 in the precursor CaCO 3 , equivalent to 9 kg of CO 2(g) per t of Ca(OH) 2 ) within an aqueous flowelectrolysis/ pH-swing process that coproduces hydrogen (H 2(g) ) and oxygen (O 2(g) ). Because Ca(OH) 2 is a zero-carbon precursor for cement and lime production, this approach represents a significant advancement in the production of zero-carbon cement. The Zero CArbon Lime (ZeroCAL) process includes dissolution, separation/recovery, and electrolysis stages according to the following steps: (Step 1) chelator (e.g., ethylenediaminetetraacetic acid, EDTA)-promoted dissolution of CaCO 3 and complexation of Ca 2+ under basic (>pH 9) conditions, (Step 2a) Ca enrichment and separation using nanofiltration (NF), which allows separation of the Ca-EDTA complex from the accompanying bicarbonate (HCO 3 – ) species, (Step 2b) acidity-promoted decomplexation of Ca from EDTA, which allows near-complete chelator recovery and the formation of a Ca-enriched stream, and (Step 3) rapid precipitation of Ca(OH) 2 from the Ca-enriched stream using electrolytically produced alkalinity. These reactions can be conducted in a seawater matrix yielding coproducts including hydrochloric acid (HCl) and sodium bicarbonate (NaHCO 3 ), resulting from electrolysis and limestone dissolution, respectively. Careful analysis of the reaction stoichiometries and energy balances indicates that approximately 1.35 t of CaCO 3 , 1.09 t of water, 0.79 t of sodium chloride (NaCl), and ~2 MWh of electrical energy are required to produce 1 t of Ca(OH) 2 , with significant opportunity for process intensification. This approach has major implications for decarbonizing cement production within a paradigm that emphasizes the use of existing cement plants and electrification of industrial operations, while also creating approaches for alkalinity production that enable cost-effective and scalable CO 2 mineralization via Ca(OH) 2 carbonation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Impacts of anthropogenic gadolinium on the activity of the ammonia oxidizing bacterium Nitrosomonas europaea

Widespread use of gadolinium-based contrast agents in medical imaging has resulted in increased Gd inputs to municipal wastewater treatment plants. Others have reported that typical wastewater treatment does not attenuate Gd, resulting in discharges to natural waters. However, whether elevated Gd impacts the performance of biological treatment has not been investigated. We examined whether gadolinium chloride or Gd chelated with diethylenetriaminepentaacetic acid (DTPA) affected the activity of the model nitrifying bacterium Nitrosomonas europaea. At nominal GdCl 3 additions ranging from 1 to 500 µM, no impact was observed compared to the control. Most (>98%) of the added Gd precipitated, and extracellular GdPO 4 nanoparticles were observed. When chelated with DTPA, Gd remained soluble, but no statistically significant impact on ammonia oxidation was observed until the highest concentrations tested. At 300 and 500 µM Gd-DTPA, a temporary reduction of nitrite production relative to the control (effect size 1.3 mg l -1 and 1.5 mg l -1 , respectively, at 24 h) was seen. By itself, DTPA was highly inhibitory. Modeling suggested that DTPA likely chelated other metals, but adjusting the concentrations of the most abundant metals in the medium, calcium and magnesium, indicated that lowering their free ion activities was probably not the cause of inhibition. Complexation of other essential metals was more likely. Furthermore, our studies indicate that while the low bioavailability of Gd may limit its ecosystem impacts, the role of synthetic ligands used with Gd and other rare earth elements should e considered as the production, use and disposal of these elements increases.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Multiphysics and Multiscale Modeling of Coupled Transport of Chloride Ions in Concrete

Chloride ions (Cl−)-induced corrosion is one of the main degradation mechanisms in reinforced concrete (RC) structures. In most situations, the degradation initiates with the transport of Cl− from the surface of the concrete towards the reinforcing steel. The accumulation of Cl− at the steel-concrete interface could initiate reinforcement corrosion once a threshold Cl− concentration is achieved. An accurate numerical model of the Cl− transport in concrete is required to predict the corrosion initiation in RC structures. However, existing numerical models lack a representation of the heterogenous concrete microstructure resulting from the varying environmental conditions and the indirect effect of time dependent temperature and relative humidity (RH) on the water adsorption and Cl− binding isotherms. In this study, a numerical model is developed to study the coupled transport of Cl− with heat, RH and oxygen (O2) into the concrete. The modeling of the concrete microstructure is performed using the Virtual Cement and Concrete Testing Laboratory (VCCTL) code developed by the U.S. National Institute of Standards and Technology (NIST). The concept of equivalent maturation time is utilized to eliminate the limitation of simulating concrete microstructure using VCCTL in specific environmental conditions such as adiabatic. Thus, a time-dependent concrete microstructure, which depends on the hydration reactions coupled with the temperature and RH of the environment, is achieved to study the Cl− transport. Additionally, Cl− binding isotherms, which are a function of the pH of the concrete pore solution, Cl− concentration, and weight fraction of mono-sulfate aluminate (AFm) and calcium-silicate-hydrate (C-S-H), obtained from an experimental study by the same authors are utilized to account for the Cl− binding of cement hydration products. The temperature dependent RH diffusion was considered to account for the transport of Cl− with moisture transport. The temperature and RH diffusion in the concrete domain, composite theory, and Cl− binding and water adsorption isotherms are used in combination, to estimate the ensuing Cl− diffusion field within the concrete. The coupled transport process of heat, RH, Cl−, and O2 is implemented in the Multiphysics Object-Oriented Simulation Environment (MOOSE) developed by the U.S. Idaho National Laboratory (INL). The model was verified and validated using data from multiple experimental studies with different concrete mixture proportions, curing durations, and environmental conditions. Additionally, a sensitivity analysis was performed to identify that the water-to-cement (w/c) ratio, the exposure duration, the boundary conditions: temperature, RH, surface Cl− concentration, Cl− diffusion coefficient in the capillary water, and the critical RH are the important parameters that govern the Cl− transport in RC structures. In a case study, the capabilities of the developed numerical model are demonstrated by studying the complex 2D diffusion of Cl− in a RC beam located in two different climatic regions: warm and humid weather in Galveston, Texas, and cold and dry weather in North Minnesota, Minnesota, subjected to time varying temperature, RH, and surface Cl− concentrations.

composite theory↗
DOE OSTI2020

Boron and Lithium in Calcium Sulfate Veins: Tracking Precipitation of Diagenetic Materials in Vera Rubin Ridge, Gale Crater

The NASA Curiosity rover's ChemCam instrument suite has detected boron in calcium-sulfate-filled fractures throughout the sedimentary strata of Gale crater including Vera Rubin ridge. The presence of elevated B concentration provides insights into Martian subsurface aqueous processes. Here, we extend the data set of B in Ca-sulfate veins across Gale crater, comparing the detection frequency and relative abundances with Li. We report 33 new detections of B within veins analyzed between Sols 1548 and 2311 where detections increase in Pettegrove Point and Jura members, which form Vera Rubin ridge. The presence of B and Li in the Ca-sulfate veins is possibly due to dissolution of preexisting B in clays of the bedrock by acids or neutral water and redistribution of the elements into the veins. Elevated frequency of B detection in veins of Gale crater correlates with presence of dehydration features such as desiccation cracks, altered clay minerals and detections of evaporites such as Mg-sulfates and chloride salts in the host rocks. The increased observations of B also coincide with decreased Li concentration in the veins (average Li concentration of veins drops by ~15 ppm). Boron and Li have varying solubilities, and Li does not form salts as readily upon dehydration as B, causing it to remain in the solution. So the weak negative correlation between B and Li may reflect the crystallization sequence during dehydration on Vera Rubin ridge.

58 GEOSCIENCES↗
DOE OSTI2020

Studies on the Encapsulation of Brine Generated from a Process Using Selective Electrodialysis Reversal

This topical report summarizes the laboratory testing, geochemical modeling, and mineralogical testing conducted to examine the efficacy of wastewater encapsulation for the brine generated from the Saltworks Flex electrodialysis reversal technology. Within the laboratory testing, the short- and long-term physical properties of seven separate mix designs were examined along with the leaching of each mix design. Additionally, geochemical thermodynamic modeling was used along with mineralogical analyses to help gain a fundamental understanding of the chemistry involved in the encapsulation process. Encapsulation is a process that results in the immobilization of constituents of interest by creating an engineered material that contains the waste within its matrix, both physically and chemically, in such a manner that the receiving environment is protected from adverse effects. Within the context of this study, encapsulation mix designs involved mixing the Saltworks brine with fly ash and various additives, principally lime (calcium oxide) and cement, to form a paste that eventually sets and hardens into a monolith upon placement in a landfill. Moisture conditioning fly ash with wastewater sources for on-site landfill disposal is a process that is in use at some sites and has been presented as a viable option to dispose of liquid wastes. However, because chemical reactions that can lead to sequestration of constituents of interest are not optimized, leaching can occur. Therefore, in this study, mixes were created to mimic moisture conditioning, as well as engineered pastes of varying mix designs. The study found that engineered encapsulation mixes provide significant resistance to leaching compared to moisture conditioning alone. The best performing encapsulation mix used lime as the additive, which proved superior to the use of cement. After 90 days of curing, this encapsulated mix was 5.5 times stronger than the moisture conditioned mix. Additionally, this mix exhibited an approximate 2.5 order of magnitude drop in hydraulic conductivity compared to the moisture conditioned mix. When comparing leaching, nearly all the chloride was found to evolve from the moisture conditioned mix, whereas only 6.7% of the chlorine contained in the best performing encapsulated mix leached out. Mineralogical analysis via X-ray diffraction (XRD) showed a significant concentration of the chloride sequestering mineral, Friedel’s salt, in the best performing encapsulation mix, whereas none was observed in the moisture conditioned mix, pointing to it being the primary chemical mechanism for chloride retention, along with the physical impermeability of the material. With respect to the modeling study, the model was successful in predicting the presence of most mineral phases observed in the XRD analysis.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS2016

Reactions Involving Calcium and Magnesium Sulfates as Potential Sources of Sulfur Dioxide During MSL SAM Evolved Gas Analyses

The Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments on the Mars Science Laboratory (MSL) have analyzed several subsamples of <150 micron fines from ten sites at Gale Crater. Three were in Yellowknife Bay: the Rocknest aeolian bedform (RN) and drilled Sheepbed mudstone from sites John Klein (JK) and Cumberland (CB). One was drilled from the Windjana (WJ) site on a sandstone of the Kimberly formation. Four were drilled from sites Confidence Hills (CH), Mojave (MJ), Telegraph Peak (TP) and Buckskin (BK) of the Murray Formation at the base of Mt. Sharp. Two were drilled from sandstones of the Stimson formation targeting relatively unaltered (Big Sky, BY) and then altered (Greenhorn, GH) material associated with a light colored fracture zone. CheMin analyses provided quantitative sample mineralogy. SAM's evolved gas analysis mass spectrometry (EGA-MS) detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases. This contribution will focus on evolved SO2. All samples evolved SO2 above 500 C. The shapes of the SO2 evolution traces with temperature vary between samples but most have at least two "peaks' within the wide high temperature evolution, from approx. 500-700 and approx. 700-860 C (Fig. 1). In many cases, the only sulfur minerals detected with CheMin were Ca sulfates (e.g., RN and GH), which should thermally decompose at temperatures above those obtainable by SAM (>860 C). Sulfides or Fe sulfates were detected by CheMin (e.g., CB, MJ, BK) and could contribute to the high temperature SO2 evolution, but in most cases they are not present in enough abundance to account for all of the SO2. This additional SO2 could be largely associated with x-ray amorphous material, which comprises a significant portion of all samples. It can also be attributed to trace S phases present below the CheMin detection limit, or to reactions which lower the temperatures of SO2 evolution from sulfates that are typically expected to thermally decompose at temperatures outside the SAM temperature range (e.g., Ca and Mg sulfates). Here we discuss the results of SAM-like laboratory analyses targeted at understanding this last possibility, focused on understanding if reactions of HCl or an HCl evolving phase (oxychlorine phases, chlorides, etc.) and Ca and Mg sulfates can result in SO2 evolution in the SAM temperature range.

McAdam, A. C.↗