SEARCH · Search NASA
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Special reagent consists of 1 part 90% lactic acid, 1 part 70% nitric acid, and 4 part, 37% hydrochloric acid. Solution etches parent and weld metals at same rate, without overetching. Underlying grain structure of both metals is revealed.
In this study, three different mineral acids were substituted for sulfuric acid (H2SO4) in the urine stabilizer solution to eliminate the excess of sulfate ions in pretreated urine and assess the impact on maximum water recovery to avoid precipitation of minerals during distillation. The study evaluated replacing 98% sulfuric acid with 85% phosphoric acid (H3PO4), 37% hydrochloric acid (HCl), or 70% nitric acid (HNO3). The effect of lowering the oxidizer concentration in the pretreatment formulation also was studied. This paper summarizes the test results, defines candidate formulations for further study, and specifies the injection masses required to stabilize urine and minimize the risk of mineral precipitation during distillation. In the first test with a brine ersatz acidified with different acids, the solubility of calcium in gypsum saturated solutions was measured. The solubility of gypsum was doubled in the brines acidified with the alternative acids compared to sulfuric acid. In a second series of tests, the alternative acid pretreatment concentrations were effective at preventing precipitation of gypsum and other minerals up to 85% water recovery from 95th-percentile pretreated, augmented urine. Based on test results, phosphoric acid is recommended as the safest alternative to sulfuric acid. It also is recommended that the injected mass concentration of chromium trioxide solution be reduced by 75% to minimize liquid resupply mass by about 50%, reduce toxicity of brines, and reduce the concentration of organic acids in distillate. The new stabilizer solution formulations and required doses to stabilize urine and prevent precipitation of minerals up to 85% water recovery are given. The formulations in this study were tested on a limited number of artificially augmented urine batches collected from employees at the Johnson Space Center (JSC). This study successfully demonstrated that the desired physical and chemical stability of pretreated urine and brines can be achieved using alternate pretreatment formulations under laboratory conditions. Additional testing and hazard assessments will be required to determine the feasibility of utilizing the proposed urine pretreatment formulations on ISS.
Excellent surface finishes and tolerances are achieved using two formulations. Solution A gives finish of 3.17 micrometers after milling at 57 to 63 deg C. Constituents of A are: Hydrofluoric acid (70%), 5,8 oz/gal; nitric acid (40-42) degrees Baume), 40 oz/gal. Alternative solution gives 2.16 micrometer finish, and differs from A by addition of 7% phosphoric acid. Formulations eliminate channeling at root fillets, dishing, island formation, and overhangs.
Presentation on the NASA and ESA Collaboration on Hexavalent Chrome Free Coatings project. Project is in response to a Memorandum of Understanding between NASA and ESA Concerning Cooperation in the Field of Space Transportation - signed September 11, 2009. The National Aeronautics and Space Administration (NASA) and the European Space Agency (ESA) have expressed mutual interest in pursuing cooperation in the areas of evaluating hexavalent chrome-free coatings, environmentally-preferable coatings for maintenance of launch facilities and ground support equipment, citric acid as an alternative to nitric acid for passivation of stainless steel alloys.
Satellite observations of polar stratospheric clouds (PSCs) over Antarctica in June 2003 revealed small nitric acid trihydrate (NAT) particles forming suddenly along the vortex edge. Models suggest the trigger was mountain waves over the Antarctic Peninsula (AP) forming ice for NAT nucleation. We test this hypothesis by analyzing perturbations in stratospheric radiances from the Atmospheric Infrared Sounder (AIRS). AIRS data show mountain waves over the AP on 10-14 June, with no resolved wave activity before or after. Peak wave temperature amplitudes derived from independent 40 hPa channels all return values of 10-12 K, in agreement with values used to model this NAT event. These observations support a NAT wake from a small region of mountain wave activity over the AP as the source of this circumpolar NAT outbreak.
The objectives of this project are to: define the chemical and physical processes leading to stratospheric ozone change that involve polar stratospheric clouds (PSCS) and the reactions occurring on the surfaces of PSC particles; study the formation processes, and the physical and chemical properties of PSCS, that are relevant to atmospheric chemistry and to the interpretation of field measurements taken during polar stratosphere missions; develop quantitative models describing PSC microphysics and heterogeneous chemical processes; assimilate laboratory and field data into these models; and calculate the extent of chemical processing on PSCs and the impact of specific microphysical processes on polar composition and ozone depletion. During the course of the project, a new coupled microphysics/physical-chemistry/ photochemistry model for stratospheric sulfate aerosols and nitric acid and ice PSCs was developed and applied to analyze data collected during NASA's Arctic Airborne Stratospheric Expedition-II (AASE-II) and other missions. In this model, detailed treatments of multicomponent sulfate aerosol physical chemistry, sulfate aerosol microphysics, polar stratospheric cloud microphysics, PSC ice surface chemistry, as well as homogeneous gas-phase chemistry were included for the first time. In recent studies focusing on AASE measurements, the PSC model was used to analyze specific measurements from an aircraft deployment of an aerosol impactor, FSSP, and NO(y) detector. The calculated results are in excellent agreement with observations for particle volumes as well as NO(y) concentrations, thus confirming the importance of supercooled sulfate/nitrate droplets in PSC formation. The same model has been applied to perform a statistical study of PSC properties in the Northern Hemisphere using several hundred high-latitude air parcel trajectories obtained from Goddard. The rates of ozone depletion along trajectories with different meteorological histories are presently being systematically evaluated to identify the principal relationships between ozone loss and aerosol state. Under this project, we formulated a detailed quantitative model that predicts the multicomponent composition of sulfate aerosols under stratospheric conditions, including sulfuric, nitric, hydrochloric, hydrofluoric and hydrobromic acids. This work defined for the first time the behavior of liquid ternary-system type-1b PSCS. The model also allows the compositions and reactivities of sulfate aerosols to be calculated over the entire range of environmental conditions encountered in the stratosphere (and has been incorporated into a trajectory/microphysics model-see above). Important conclusions that derived from this work over the last few years include the following: the HNO3 content of liquid-state aerosols dominate PSCs below about 195 K; the freezing of nitric acid ice from sulfate aerosol solutions is likely to occur within a few degrees K of the water vapor frost point; the uptake and reactions of HCl in liquid aerosols is a critical component of PSC heterogeneous chemistry. In a related application of this work, the inefficiency of chlorine injection into the stratosphere during major volcanic eruptions was explained on the basis of nucleation of sulfuric acid aerosols in rising volcanic plumes leading to the formation of supercooled water droplets on these aerosols, which efficiently scavenges HCl via precipitation.
We report here measurements of the acidic gases nitric (HNO3), formic (HCOOH), and acetic (CH3COOH) over the western Pacific basin during the February-March 1994 Pacific Exploratory Mission-West (PEM-West B). These data were obtained aboard the NASA DC-8 research aircraft as it flew missions in the altitude range of 0.3 - 12.5 km over equatorial regions near Guam and then further westward encompassing the entire Pacific Rim arc. Aged marine air over the equatorial Pacific generally exhibited mixing ratios of acidic gases less than 100 parts per trillion by volume (pptv). Near the Asian continent, discrete plumes encountered below 6 km altitude contained up to 8 parts per billion by volume (ppbv) HNO3 and 10 ppbv HCOOH and CH3COOH. Overall there was a general correlation between mixing ratios of acidic gases with those of CO, C2H2, and C2Cl4, indicative of emissions from combustion and industrial sources. The latitudinal distributions of HNO3 and CO showed that the largest mixing ratios were centered around 15 deg N, while HCOOH, CH3COOH, and C2Cl4 peaked at 25 deg N. The mixing ratios of HCOOH and CH3COOH were highly correlated (r(sup 2) = 0.87) below 6 km altitude, with a slope (0.89) characteristic of the nongrowing season at midlatitudes in the northern hemisphere. Above 6 km altitude, HCOOH and CH3COOH were marginally correlated (r(sup 2) = 0.50), and plumes well defined by CO, C2H2, and C2Cl4 were depleted in acidic gases, most likely due to scavenging during vertical transport of air masses through convective cloud systems over the Asian continent. In stratospheric air masses, HNO, mixing ratios were several parts per billion by volume (ppbv), yielding relationships with 03 and N2O consistent with those previously reported for NO(y).
The direct dissolution of voloxidized used nuclear fuel (UNF) into an organic solution–comprised of diluent and specialized extractants–poses a promising alternative to the traditional liquid–liquid solvent extraction approach to reprocessing UNF. However, moving to direct dissolution removes the presence of a concentrated nitric acid aqueous phase, which has been shown to significantly influence the radiolytic longevity of extractants in conventional extraction flowsheets. Given the limited knowledge of radiation effects under direct dissolution conditions, here we present a time-resolved and dose-accumulation study on the impact of direct dissolution conditions on the radiolytic longevity of two candidate butyramide extractants, N,N-di(2-ethylhexyl) butyramide (DEHBA) and N,N-di(2-ethylhexyl)isobutyramide (DEHiBA), in pre-equilibrated n-dodecane solvent in the presence and absence of process-relevant metal ions, specifically, uranium and rhenium. Loss G(DEHBA) and G(DEHiBA) values were found to be comparable to each other, with an average of 0.37 ± 0.02 μmol J –1 , and to previous data from the γ irradiation of DEHBA and DEHiBA under conventional solvent extraction conditions. Rhenium, and by extension technetium, extraction had a modest decrease (~10%) in the overall radiolytic stability of DEHiBA only, despite >2× observed increases in chemical kinetic reactivity of the corresponding complexes with the n-dodecane radical cation. Uranium loading, on the other hand, significantly improved the lifetime of both ligands (>30%) under γ irradiation, with a greater stabilization observed for DEHBA over DEHiBA. The observed radioprotective effect afforded by uranium loading is fortuitous for the longevity of direct dissolution solvent.
A theory for the formation of frozen aerosol particles in the Antarctic stratosphere was developed and applied to the formation of polar stratospheric clouds. The theory suggests that the condensed ice particles are composed primarily of nitric acid and water, with small admixtures of sulfuric and hydrochloric acids in solid solution. The proposed particle formation mechanism is in agreement with the magnitude and seasonal behavior of the optical extinction observed in the winter polar stratosphere.
During the period July, 1977 to September, 1979, rainfall was collected in the vicinity of the Kennedy Space Center and subjected to appropriate chemical analysis for purposes of characterization of general composition and acidity. Results obtained form the basis for future comparisons, should significant alteration of the chemical composition of rain occur during the space shuttle era. Acidity extremes calculated on a monthly basis from event samples collected from five sites within a 200 sq km area varied from pH 5.1 in November, 1977, and April, 1978 to pH 4.3 in July, 1978 and July, 1979. Weighted average pH for the entire period was 4.55. Acidity was due to the presence of sulfuric and nitric acids. The mole ratio of excess SO4(-2):NO3(-) was typically greater than one. Monthly weighted average Cl(-) concentrations ranged from 20-240 micromoles/liter. The Cl(-):Na(+) ratio was slightly lower than that present in sea water.
The ways in which clays have been utilized in studies of prebiological chemistry are reviewed, and an assessment is given of the possible role of clays in prebiological systems. The adsorption of organic molecules on clays has been demonstrated, as has the synthesis of bioorganic monomers in the presence of clays. For instance, amino acids, purines and pyrimidines have been obtained from carbon monoxide and nitric acid in the presence of clays at relatively high temperatures (250-325 C). The oligomerization of biochemical monomers, mediated by clays, has also been shown to result in the formation of polymer molecules basic to life. Clays have also been found to affect the condensation of mononucleotides to oligonucleotides.
This report describes characterization of nitrogen species (nitrate, nitrite, ammonia) in aqueous and solid phases in cores taken in borehole D0220 (well 299-E25-245) under crib 216-A-37-1 at the Hanford Site in 2022 to evaluate (a) the types of nitrogen species currently in the vadose zone and (b) the migration of nitrogen species in the vadose zone. Ammonia and tritium from PUREX decladding condensate were sporadically discharged to the crib from 1977 to 1989. During discharge operations, the estimated travel time through the vadose zone to groundwater was 2.5 to 9 months. By 2003, a characterization borehole (C4106) showed residual pore water with elevated tritium and nitrate in the first 100 ft of the vadose zone, which is likely from the crib. However, there was significantly more nitrate present at the shallowest depth (15 to 22 ft), which may indicate a different source for nitrate, such as adsorbed ammonia slowly being oxidized or nitrogen species precipitates slowly dissolving. In this study, more extensive nitrogen species characterization was done on D0220 cores (drilled in 2022) at 40- and 262-ft depths, which included (a) aqueous nitrate, nitrite, and tritium; (b) adsorbed ammonia; (c) nitrogen in carbonates (or other minerals dissolved in acidic acid); (d) nitrogen in iron oxides (or other minerals dissolved in oxalic acid); and (e) nitrogen in hard-to-extract minerals (minerals dissolved in nitric acid). High pore water nitrate (226 to 331 mg/L) at 40-ft depth measured in D0220 (2022) compared to 60 mg/L at 40-ft depth in C4106 (2003) may indicate nitrate is migrating deeper. Tritium concentrations (pore water 132,000 to 148,000 pCi/L) measured in D0220 at 40-ft depth in 2022 were considerably higher than in C4106 at 40-ft depth (160 pCi/L). Additional nitrogen species mass was present in adsorbed and precipitated phases in D0220 cores. Low adsorbed ammonia was measured at 40.1- and 261.7-ft depths. Low concentrations of carbonate associated nitrogen and iron oxide-associated nitrogen were present at 40.1 and 40.6 ft depths. Nitrogen species in solid phase extractions indicate nitrogen precipitates or aqueous nitrate or ammonia trapped in sediment microfractures that are coated by precipitates. Overall, the nitrogen species and tritium characterization at two depths in D0220 showed that additional nitrogen species were present in the vadose zone. In addition, elevated pore water nitrate in D0220 at 40 ft depth from 2022 may indicate vertical migration compared to C4106 nitrate profile from 2003. Analysis of additional depths in D0220 and spatial variability of the nitrate plume along the length of the crib (from surface electrical resistivity) would be extremely useful for this comparison.
Hollow tubes coated with tungstic acid have been shown to be of value in the determination of ammonia and nitric acid in ambient air. Practical application of this technique was demonstrated utilizing an automated sampling system for in-flight collection and analysis of atmospheric samples. Due to time constraints these previous measurements were performed on tubes that had not been well characterized in the laboratory. As a result the experimental precision could not be accurately estimated. Since the technique was being compared to other techniques for measuring these compounds, it became necessary to perform laboratory tests which would establish the reliability of the technique. This report is a summary of these laboratory experiments as they are applied to the determination of ambient ammonia concentration.
Stratospheric aerosols affect the atmospheric energy balance by scattering and absorbing solar and terrestrial radiation. They also can alter stratospheric chemical cycles by catalyzing heterogeneous reactions which markedly perturb odd nitrogen, chlorine and ozone levels. Aerosol measurements by satellites began in NASA in 1975 with the Stratospheric Aerosol Measurement (SAM) program, to be followed by the Stratospheric Aerosol and Gas Experiment (SAGE) starting in 1979. Both programs employ the solar occultation, or Earth limb extinction, techniques. Major results of these activities include the discovery of polar stratospheric clouds (PSCs) in both hemispheres in winter, illustrations of the impacts of major (El Chichon 1982 and Pinatubo 1991) eruptions, and detection of a negative global trend in lower stratospheric/upper tropospheric aerosol extinction. This latter result can be considered a triumph of successful worldwide sulfur emission controls. The SAGE record will be continued and improved by SAGE III, currently scheduled for multiple launches beginning in 2000 as part of the Earth Observing System (EOS). The satellite program has been supplemented by in situ measurements aboard the ER-2 (20 km ceiling) since 1974, and from the DC-8 (13 km ceiling) aircraft beginning in 1989. Collection by wire impactors and subsequent electron microscopic and X-ray energy-dispersive analyses, and optical particle spectrometry have been the principle techniques. Major findings are: (1) The stratospheric background aerosol consists of dilute sulfuric acid droplets of around 0.1 micrometer modal diameter at concentration of tens to hundreds of monograms per cubic meter; (2) Soot from aircraft amounts to a fraction of one percent of the background total aerosol; (3) Volcanic eruptions perturb the sulfuric acid, but not the soot, aerosol abundance by several orders of magnitude; (4) PSCs contain nitric acid at temperatures below 195K, supporting chemical hypotheses implicating manmade fluorocarbons as cause of the --'ozone hole'; (5) The current soot loading is too small to be of environmental (radiative and chemical) consequence. However, the fractal nature of soot distinguishes it aerodynamically and radiatively from sulfuric acid droplets such that its stratospheric residence time is longer, mainly because of vertical transport against gravity due to gravito-photophoretic forces. Thus it may accumulate and become of environmental concern in the future.
Progress to date in an ongoing study to analyze and model emissions leaving a proposed High Speed Civil Transport (HSCT) from when the exhaust gases leave the engine until they are deposited at atmospheric scales in the stratosphere is documented. A kinetic condensation model was implemented to predict heterogeneous condensation in the plume regime behind an HSCT flying in the lower stratosphere. Simulations were performed to illustrate the parametric dependence of contrail droplet growth on the exhaust condensation nuclei number density and size distribution. Model results indicate that the condensation of water vapor is strongly dependent on the number density of activated CN. Incorporation of estimates for dilution factors into a Lagrangian box model of the far-wake regime with scale-dependent diffusion indicates negligible decrease in ozone and enhancement of water concentrations of 6-13 times background, which decrease rapidly over 1-3 days. Radiative calculations indicate a net differential cooling rate of the plume about 3K/day at the beginning of the wake regime, with a total subsidence ranging between 0.4 and 1 km. Results from the Lagrangian plume model were used to estimate the effect of repeated superposition of aircraft plumes on the concentrations of water and NO(y) along a flight corridor. Results of laboratory studies of heterogeneous chemistry are also described. Kinetics of HCl, N2O5 and ClONO2 uptake on liquid sulfuric acid were measured as a function of composition and temperature. Refined measurements of the thermodynamics of nitric acid hydrates indicate that metastable dihydrate may play a role in the nucleation of more stable trihydrates PSC's.
The classical theory of homogeneous nucleation was used to calculate the freezing rate of sulfuric acid solution aerosols under stratospheric conditions. The freezing of stratospheric aerosols would be important for the nucleation of nitric acid trihydrate particles in the Arctic and Antarctic stratospheres. In addition, the rate of heterogeneous chemical reactions on stratospheric aerosols may be very sensitive to their state. The calculations indicate that homogeneous freezing nucleation of pure water ice in the stratospheric solution droplets would occur at temperatures below about 192 K. However, the physical properties of H2SO4 solution at such low temperatures are not well known, and it is possible that sulfuric acid aerosols will freeze out at temperatures ranging from about 180 to 195 K. It is also shown that the temperature at which the aerosols freeze is nearly independent of their size.
Methods and apparatus utilizing hydrogen peroxide are useful to reduce SOx and mercury (or other heavy metal) emissions from combustion flue gas streams. The methods and apparatus may further be modified to reduce NOx emissions. Continuous concentration of hydrogen peroxide to levels approaching or exceeding propellant-grade hydrogen peroxide facilitates increased system efficiency. In this manner, combustion flue gas streams can be treated for the removal of SOx and heavy metals, while isolating useful by-products streams of sulfuric acid as well as solids for the recovery of the heavy metals. Where removal of NOx emissions is included, nitric acid may also be isolated for use in fertilizer or other industrial applications.
Here, the selective dissolution of uranium metal from its mixtures with UO 2 was studied to establish a simple and rapid quantitative method. Uranium metal was found to selectively dissolve as U(IV) into a solution of phosphoric and hydrochloric acids, with quantitative dissolution occurring within 1 h. Total dissolution of uranium as U(VI) could then be obtained by nitric acid addition and heating for 0.5–1 h. Analysis of the resulting U(IV) and U(VI) solutions by ICP-OES or UV–Vis spectroscopy yielded uranium metal-to-UO 2 ratios with an accuracy of ± 10% or better. Accuracy of the ICP-OES method was slightly better than UV–Vis, but the simplicity of the latter makes it an attractive option for some applications.