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NASA NTRS2016

Chromophores from photolyzed ammonia reacting with acetylene: Application to Jupiters Great Red Spot

The high altitude of Jupiter's Great Red Spot (GRS) may enhance the upward flux of gaseous ammonia (NH3 ) into the high troposphere, where NH3 molecules can be photodissociated and initiate a chain of chemical reactions with downwelling acetylene molecules (C2H2 ). These reactions, experimentally studied earlier by (Ferris and Ishikawa [1987] Nature 326, 777-778) and (Ferris and Ishikawa [1988] J. Amer. Chem. Soc. 110, 4306-4312), produce chromophores that absorb in the visible and ultraviolet regions. In this work we photolyzed mixtures of NH3 and C2H2 using ultraviolet radiation with a wavelength of 214 nm and measured the spectral transmission of the deposited films in the visible region (400-740 nm). From these transmission data we estimated the imaginary indices of refraction. Assuming that ammonia grains at the top of the GRS clouds are coated with this material, we performed layered sphere and radiative transfer calculations to predict GRS reflection spectra. Comparison of those results with observed and previously unreported Cassini visible spectra and with true-color images of the GRS show that the unknown GRS chromophore is spectrally consistent with the coupled NH3-C2H2 photochemical products produced in our laboratory experiments. Using high-resolution mass spectrometry and infrared spectroscopy we infer that the chromophore-containing residue is composed of aliphatic azine, azo, and diazo compounds.

Jupiter↗
NASA NTRSDate not supplied

Predicting the Seawater Chemistry of an Ocean World Using Machine Learning on Isotopic Measurements of Volatile CO2

Introduction: Given the long time intervals required for data transmission to and from ocean worlds targets, low bandwidth for data transmission, time required for data processing and analysis, and potentially extreme radiation environments (e.g., Europa), it is clear that ocean worlds missions will need more autonomous flight instruments and software in order to achieve established science goals. Protracted time intervals for data analysis (e.g., Europa Lander) strongly motivates the development of rapid, consistent and streamlined methods for interpreting data from flight mass spectrometers to e.g., determine how mass spectra from a plume or surface liquid/ice relates to the surface/subsurface. Since mass spectrometry also has the potential to correctly identify biosignatures[1], it is imperative that such methods for interpreting data are consistent and accurate. We used 848 isotope ratio mass spectra from laboratory analyses of CO2 that interacted with ocean worlds-relevant seawaters as a ‘training’ dataset for ‘unsupervised’ machine learning. In unsupervised learning, characteristics of the data are not labeled or linked, and any similarities found only result from the neural network. CO2 isotopologues analyzed for this dataset mimic the remote measurements of CO2 by a flight mass spectrometer, and are detailed in Theiling [2]. From this dataset, we used measured features of the spectra, such as retention time, intensity, and (isotopologue) mass ratios as inputs for our autoencoder neural network. Our neural network was trained to find similarities in these and other spectral features for seawaters of a particular composition and amount of initial CO2. Successful training then created an output of these similarities for various seawaters, which included MgSO4, Na2SO4, NaCl, MgCl2, KCl, and NaHCO3, and combinations of these salts. We then applied dimensionality reduction techniques such as Principal Component Analysis (PCA), T-Distributed Stochastic Neighbor Embedding (TSNE), and Uniform Manifold Approximation and Projection (UMAP) to demonstrate latent data features as a two-dimensional projection in a unitless, high-dimensional space. In this projection, a data point represents the combined effect of spectral features such as intensity, retention time, and isotope ratio. Our initial UMAP demonstrates data clustering (organization of the data by the neural network) based on the amount of CO2 that had initially interacted with each seawater. Further training using more ‘supervised’ learning techniques demonstrate strong clustering of preliminary data based on initial CO2 concentration, seawater chemical composition, and ionic strength (salinity). Our preliminary work therefore suggests that machine learning has the potential to identify compositional variants of an ocean world seawater based on mass spectra from volatile CO2 measurements. Acknowledgments: This work was funded through a Strategic Task Group at NASA Goddard Space Flight Center. The training dataset was collected through funding from the Oklahoma Space Grant Consortium. References: [1] Pappalardo, R. et al. (2013) Astrobiology, 13, 740–773. [2] Theiling (2020) Icarus, 114216.

Europa↗
NASA NTRSDate not supplied

Supercritical Water Oxidation: Testing of Ersatz Wastewater

Supercritical Water Oxidation (SCWO) technology is under consideration by NASA for treatment of wastewater and other wet waste streams. The dramatic changes in water's thermophysical properties near its critical point (374◦C and 22 MPa) result in nearly complete solubility of organics and gases. The absence of inter–phase transport processes and phase separation results in dramatically reduced reaction timescales and the elimination of complications of two–phase transport and processing in reduced gravity. Other advantages are that the product streams are microbially inert,benign, amenable to resource recovery and organic waste. This paper first described the design and construction of tubular SCWO reactor built at NASA Glenn. It consists of separate wastewater and oxidizer inlets, which are independently heated and pressurized to conditions approaching the critical point of water. These flows enter a reactor chamber having a volume of 62 ml. The reactor section is heated to the desired temperature in the range of 450 ◦C – 650 ◦C. A pressure regulator maintains the operating pressure nominally between 27.6 MPa and 28.3 MPa. The reacted fluid is captured downstream of the pressure regulator during an experiment run. A separate vent line may also be used for collection of the effluent. Next, the results of SCWO experiments using both a representative organic (ethanol) as well as a wastewater simulant provided by NASA Ames are presented. Raman analysis of the pre–reacted and post–reacted solutions are presented. Finally, initial efforts on supplementary chemical kinetics modeling of ethanol oxidation with and without inclusion of a nitrogenous compounds (ammonia) are presented.

Michael C Hicks↗
NASA NTRSDate not supplied

Chemical Reactivity of In-Situ Lunar Dust for Biotoxicity Assessment

Introduction: How does the chemical reactivity of in-situ lunar dust compare to Apollo samples currently stored in curation facilities here on Earth? Essential investigations of this question will help us to further mitigate exploration risks for future human explorers on the Moon and will also provide critical information for astrobiologists and space biologists using the Moon for scientific inquiry. Discussion: Apollo 14 dust biotoxicity studies, carried out by the NASA Lunar Airborne Dust Toxici-ty Assessment Group (LADTAG), included numerous physiochemical studies[1] and cellular and animal ex-periments. Intratracheal instillation [2] and inhalation studies [3] in rats both showed Apollo 14 dust to be intermediate in toxicity compared to low-tox titanium dusts and high-tox quartz dusts of similar particle siz-es. The collective results were used in models [4] to establish a safe exposure limit for astronauts [5]. Alt-hough LADTAG took extensive steps to preserve what chemical reactivity may still have existed in the sam-ples, it is simply unknown if they possessed true in-situ chemical reactivity or if that reactivity has de-cayed. Initial gas loss on collection and other altera-tions, and even intermittent exposure to Earth-normal conditions during subsequent decades of handling, obscure a forensic reconstruction of the initial state. Because a mineral dust’s chemical reactivity influ-ences its biotoxicity [6], researchers have developed methods to “activate” lunar dust and simulants [7][8]. Past studies that modeled impact processes and radia-tion [9] in the lunar environment suggest that in-situ lunar dust is likely to be more chemically reactive than Earth-exposed samples. Because of these results, in-situ measurements are warranted [10]. Other studies have examined the hydroxyl generating capability of iron bearing mineral phases [11][12] and further em-phasize the role iron plays in chemical reactivity of lunar material, as well as decay of chemical reactivity in mineral dusts [12]. Recent observations of the lunar surface reveal the presence of hematite [13], a finding that further supports the hypothesis that in-situ lunar dust is reactive. Since the lunar surface is heterogene-ous, dust biotoxicity is expected to vary from site to site [14] due to particle size, mineralogy, physical characteristics, degree of space weathering, and chemi-cal reactivity (Figure 1). This circumstance dictates dust assessments at a suite of lunar sites enabled by upcoming NASA and commercial lunar payload ser-vices (CLPS) opportunities. Dose, location, and dura-tion of particle exposure will also affect biological responses. In-situ chemical reactivity measurements can inform cross-cutting collaborative research cam-paigns such as astrobiology studies examining regolith interactions with organisms and its ability to preserve chemical and structural biomarkers, as well as space biology investigations that examine regolith-microbe interactions relating to life support systems, plant growth, biomining, and development of regolith bio-composites. Figure 1: Environment conditions on the lunar surface that may alter regolith reactivity. Summary A series of in-situ measurements of lu-nar dust free radical chemistry at future Artemis and CLPS landing sites, combined with LADTAG-like studies of freshly collected lunar dust specimens, will reveal the true chemical reactivity of in-situ lunar dust and generate scientific data that can be compared to the chemical reactivity and biotoxicity of samples from Apollo landing sites. Furthermore, results from in situ measurements and biotoxicity studies of freshly col-lected specimens can also be used to validate, or re-quire revision of, the current astronaut permissible exposure limit [15]. References: [1] McKay D et al (2015), Acta As-tronaut 107:163–176. [2] Rask J et al (2013), LPSC, p 3062. [3] Lam CW et al (2013), Inhal Toxicol 25:661–678. [4] James JT, et. al. (2013) , Inhal Toxicol 25:243–256. [5] Scully RR, et.al. (2013), Inhal Toxi-col 25:785–793. [6] Porter, D. W., et.al., (2002), Tox-icology 175, 63–71. [7] Wallace WT, et.al., (2009), Meteorit Planet Sci 44:961–970. [8] Wallace WT, et.al., (2010), Earth Planet Sci Lett 295:571–577. [9] Loftus D, Rask J, et.al., (2010), Earth Moon Planet 107:95–105. [10] Rask J, et.al., (2009) LEAG p 57. [11] Turci F, et.a., (2015), Astrobiology. 2015;15(5):371-380. [12] Hendrix DA, et.al., (2019), Geohealth. 2019;3(1):28-42. [13] Li, S., et.al., (2020), Science advances, 6(36), p.eaba1940. [14] Rask J. (2018), In: Cudnik B. (eds) Encyclopedia of Lunar Science. Springer, Cham. [15] Rask, J, (2020), LPI, Artemis III Sci. def. paper 2120.

chemical reactivity↗
NASA NTRS1990

Large eddy simulations and direct numerical simulations of high speed turbulent reacting flows

This research is involved with the implementation of advanced computational schemes based on large eddy simulations (LES) and direct numerical simulations (DNS) to study the phenomenon of mixing and its coupling with chemical reactions in compressible turbulent flows. In the efforts related to LES, a research program to extend the present capabilities of this method was initiated for the treatment of chemically reacting flows. In the DNS efforts, the focus is on detailed investigations of the effects of compressibility, heat release, and non-equilibrium kinetics modelings in high speed reacting flows. Emphasis was on the simulations of simple flows, namely homogeneous compressible flows, and temporally developing high speed mixing layers.

Givi, Peyman↗
NASA NTRS1991

The direct simulation of high-speed mixing-layers without and with chemical heat release

A direct numerical simulation of high speed reacting and non-reacting flows for H2-air systems is presented. The calculations are made for a convective Mach number of 0.38 with hyperbolic tangent initial profile and finite rate chemical reactions. A higher-order numerical method is used in time accurate mode to time advance the solution to a statistical steady state. About 600 time slices of all the variables are then stored for statistical analysis. It is shown that most of the problems of high-speed combustion with air are characterized by relatively weak heat release. The present study shows that: (1) the convective speed is reduced by heat release by about 10 percent at this convective Mach number M(sub c) = 0.38; (2) the variation of the mean and rms fluctuation of temperature can be explained on the basis of temperature fluctuation between the flame temperature and the ambient; (3) the growth rate with heat release is reduced by 7 percent; and (4) the entrainment is reduced by 25 percent with heat release. These differences are small in comparison with incompressible flow dynamics, and are argued to be due to the reduced importance of heat release in comparison with the large enthalpy gradients resulting from the large-scale vortex dynamics. It is finally suggested that the problems of reduced mixing in high-speed flows are not severely complicated by heat release.

Sekar, B.↗
NASA NTRS1996

An Experimental Study of Ignition Effects and Flame Growth Over a Thin Solid Fuel in Low-Speed Concurrent Flow Using Drop-Tower Facilities

An experimental study of ignition and flame growth over a thin solid fuel in oxidizer flow speeds from 0 to 10 cm/sec concurrent flow was performed. This study examined the differences between ignition using a resistively heated wire (woven in a sawtooth pattern over the leading edge of the fuel), and a straight resistively heated wire augmented by a chemical ignitor doped onto the leading edge of the fuel. Results showed that the chemical system yielded non-uniform ignition bursts, while the system using only the hotwire gave more uniform ignition. At speeds up to 2.5 cm/sec, the chemical system yielded non-uniform pyrolysis fronts, while the hotwire system gave more uniform pyrolysis fronts. At speeds of 5 cm/sec or greater, both systems gave uniform pyrolysis fronts. The chemically-ignited flames tended to become too dim to see faster than the hotwire-ignited flames, and the flame lengths were observed to be shorter (after the initial burst subsided) for the chemical system for all speeds. Flame and pyrolysis element velocities were measured. Temperature profiles for selected tests were measured using thermocouples at the fuel surface and in the gas phase. Comparisons between the flame element velocities and peak temperatures recorded in these tests with calculated spread rates and peak temperatures from a steady-state model are presented. Agreement was found to be within 20% for most flame elements for nominal velocities of 5 cm/sec and 7.5 cm/sec.

Pettegrew, Richard Dale↗
NASA NTRS1972

Laser-induced gas breakdown - Spectroscopic and chemical studies.

Discussion of the results of several experimental investigations on laser-induced gas breakdown. The experiments included time-resolved spectroscopy, direct detection of H atoms with a TiO2 probe, and chemical reactions; each of them provided insight into the behavior of the medium at different times. Chemical reactions and explosions have been initiated by the laser beam when a plasma was created. No primary multiphotonic absorption and no macroscopic chemical reactions were observed below the breakdown threshold.

De Montgolfier, PH.↗
NASA NTRS1991

Jet-A reaction mechanism study for combustion application

Simplified chemical kinetic reaction mechanisms for the combustion of Jet A fuel was studied. Initially, 40 reacting species and 118 elementary chemical reactions were chosen based on a literature review. Through a sensitivity analysis with the use of LSENS General Kinetics and Sensitivity Analysis Code, 16 species and 21 elementary chemical reactions were determined from this study. This mechanism is first justified by comparison of calculated ignition delay time with the available shock tube data, then it is validated by comparison of calculated emissions from the plug flow reactor code with in-house flame tube data.

Lee, Chi-Ming↗
NASA NTRS1991

Jet-A reaction mechanism study for combustion application

Simplified chemical kinetic reaction mechanisms for the combustion of Jet A fuel are studied. Initially 40 reacting species and 118 elementary chemical reactions were chosen based on the literature review of previous works. Through a sensitivity analysis with the use of LSENS General Kinetics and Sensitivity Analysis Code, 16 species and 21 elementary chemical reactions were determined from this study. This mechanism is first justified by comparison of calculated ignition delay time with available shock tube data, then it is validated by comparison of calculated emissions from plug flow reactor code with in-house flame tube data.

Lee, Chi-Ming↗
NASA NTRS1995

Optimal lunar trajectories for a combined chemical-electric propulsion spacecraft

Spacecraft which utilize electric propulsion (EP) systems are capable of delivering a greater payload fraction compared to spacecraft using conventional chemical propulsion systems. Several researchers have investigated numerous applications of low-thrust EP including a manned Mars mission, scientific missions to the outer planets, and lunar missions. In contrast, the study of optimal combined high and low-thrust spacecraft trajectories has been limited. In response to the release of NASA's 1994 Announcement of Opportunity (AO) for Discovery class interplanetary exploration missions, a preliminary investigation of a lunar comet rendezvous mission using a solar electric propulsion (SEP) spacecraft was performed. The Discovery mission (eventually named Diana) was envisioned to be a two-phase scientific exploration mission: the first phase involved exploration of the moon and second phase involved rendezvous with a comet. The initial phase began with a chemical propulsion translunar injection and chemical insertion into a lunar orbit, followed by a low-thrust SEP transfer to a circular, polar, low-lunar orbit (LLO). After scientific data was collected at the moon, the SEP spacecraft performed a spiral lunar escape maneuver to begin the interplanetary leg of the mission. After escape from the Earth-moon system, the SEP spacecraft maneuvered in interplanetary space and performed a rendezvous with a short period comet. An initial study that demonstrated the feasibility of using EP for the lunar and comet orbit transfer was performed under the grant NAG3-1581. This final report is a continuation of the initial research efforts in support of the Discovery mission proposal that was submitted to NASA Headquarters in October 1994. Section 2 discusses the lunar orbit transfer phase of the Diana mission which involves both chemical and electric propulsion stages. Section 3 discusses the chemical lunar orbit insertion (LOI) burn optimization. Finally, section 4 presents the conclusions of this research effort.

Kluever, Craig A.↗
NASA NTRS1992

Odd oxygen formation in the laser irradiation of O2 at 248 nm - Evidence for reactions of O2 in the Herzberg states with ground state O2

Two O3 formation processes (initiation and autocatalytic) are studied in pure O2 and in O2+N2 and O2+Ar mixtures at pressures between 200 and 1600 torr and at temperatures between 298 and 370 K. Evidence is presented that the initiation process produces O3 through chemical reactions between ground state O2 and excited O2 in the Herzberg states, which are produced by the photoabsorption of O2 at 248 nm. For the autocatalytic process, the results are consistent with the proposal that the O3 formation is accelerated by photodissociating vibrationally excited O2(nu), produced in the photolysis of O3 following its initial formation. It is argued that the O2 Herzberg states and O2(nu) may play important roles in the odd oxygen chemistry in the middle atmosphere. It is estimated that the O2(A3Sigma-u(+))+O2 reaction may yield up to about 6 percent of the total odd oxygen production rate near 50 km.

Shi, Jichun↗
NASA NTRS1979

Development and testing of dry chemicals in advanced extinguishing systems for jet engine nacelle fires

The effectiveness of dry chemical in extinguishing and delaying reignition of fires resulting from hydrocarbon fuel leaking onto heated surfaces such as can occur in jet engine nacelles is studied. The commercial fire extinguishant dry chemical tried are sodium and potassium bicarbonate, carbonate, chloride, carbamate (Monnex), metal halogen, and metal hydroxycarbonate compounds. Synthetic and preparative procedures for new materials developed, a new concept of fire control by dry chemical agents, descriptions of experiment assemblages to test dry chemical fire extinguishant efficiencies in controlling fuel fires initiated by hot surfaces, comparative testing data for more than 25 chemical systems in a 'static' assemblage with no air flow across the heated surface, and similar comparative data for more than ten compounds in a dynamic system with air flows up to 350 ft/sec are presented.

Altman, R. L.↗
NASA NTRS1981

The transport of photochemical pollutants to the background troposphere

The considered investigation is concerned with the phenomena occurring as a chemically reacting plume, with specific initial concentrations of NO, NO2, O3, and hydrocarbons, emerges from an urban area and is advected to the background troposphere. A better understanding of the global NOx and hydrocarbon budgets can be realized by determining the fractions of NOx and hydrocarbons that are transported to distances far enough to be considered background. The investigation makes use of a 56-step, lumped kinetic mechanism for photochemical smog, which includes current information on pertinent chemical reactions and rate constants for the reactions.

Bazzell, C. C.↗
NASA NTRS1990

Critical evaluation of Jet-A spray combustion using propane chemical kinetics in gas turbine combustion simulated by KIVA-II

Numerical solutions of the Jet-A spray combustion were obtained by means of the KIVA-II computer code after Jet-A properties were added to the 12 chemical species the program had initially contained. Three different reaction mechanism models are considered. The first model consists of 131 reactions and 45 species; it is evaluated by comparing calculated ignition delay times with available shock tube data, and it is used in the evaluation of the other two simplified models. The simplified mechanisms consider 45 reactions and 27 species and 5 reactions and 12 species, respectively. In the prediction of pollutants NOx and CO, the full mechanism of 131 reactions is considered to be more reliable. The numerical results indicate that the variation of the maximum flame temperature is within 20 percent as compared with that of the full mechanism of 131 reactions. The chemical compositions of major components such as C3H8, H2O, O2, CO2, and N2 are of the same order of magnitude. However, the concentrations of pollutants are quite different.

Nguyen, H. L.↗
NASA NTRS2017

Spacecraft Re-Entry Impact Point Targeting Using Aerodynamic Drag

The ability to re-enter the atmosphere at a desired location is important for spacecraft containing components that may survive re-entry. While impact point targeting has traditionally been initiated through impulsive burns with chemical thrusters on large vehicles such as the Space Shuttle, and the Soyuz and Apollo capsules, many small spacecraft do not host thrusters and require an alternative means of impact point targeting to ensure that falling debris do not cause harm to persons or property. This paper discusses the use of solely aerodynamic drag force to perform this targeting. It is shown that by deploying and retracting a drag device to vary the ballistic coefficient of the spacecraft, any desired longitude and latitude on the ground can be targeted provided that the maneuvering begins early enough and the latitude is less than the inclination of the orbit. An analytical solution based on perturbations from a numerically propagated trajectory is developed to map the initial state and ballistic coefficient profile of a spacecraft to its impact point. This allows the ballistic coefficient profile necessary to reach a given target point to be rapidly calculated, making it feasible to generate the guidance for the decay trajectory onboard the spacecraft. The ability to target an impact point using aerodynamic drag will enhance the capabilities of small spacecraft and will enable larger space vehicles containing thrusters to save fuel by more effectively leveraging the available aerodynamic drag.

propagation↗
NASA NTRS1990

The effect of interplanetary trajectory options on a manned Mars aerobrake configuration

Manned Mars missions originating in low Earth orbit (LEO) in the time frame 2010 to 2025 were analyzed to identify preferred mission opportunities and their associated vehicle and trajectory characteristics. Interplanetary and Mars atmospheric trajectory options were examined under the constraints of an initial manned exploration scenario. Two chemically propelled vehicle options were considered: (1) an all propulsive configuration, and (2) a configuration which employs aerobraking at Earth and Mars with low lift/drag (L/D) shapes. Both the interplanetary trajectory options as well as the Mars atmospheric passage are addressed to provide a coupled trajectory simulation. Direct and Venus swingby interplanetary transfers with a 60 day Mars stopover are considered. The range and variation in both Earth and Mars entry velocity are also defined. Two promising mission strategies emerged from the study: (1) a 1.0 to 2.0 year Venus swingby mission, and (2) a 2.0 to 2.5 year direct mission. Through careful trajectory selection, 11 mission opportunities are identified in which the Mars entry velocity is between 6 and 10 km/sec and Earth entry velocity ranges from 11.5 to 12.5 km/sec. Simulation of the Earth return aerobraking maneuver is not performed. It is shown that a low L/D configuration is not feasible for Mars aerobraking without substantial improvements in the interplanetary navigation system. However, even with an advanced navigation system, entry corridor and aerothermal requirements restrict the number of potential mission opportunities. It is also shown that for a large blunt Mars aerobrake configuration, the effects of radiative heating can be significant at entry velocities as low as 6.2 km/sec and will grow to dominate the aerothermal environment at entry velocities above 8.5 km/sec. Despite the additional system complexity associated with an aerobraking vehicle, the use of aerobraking was shown to significantly lower the required initial LEO weight. In comparison with an all propulsive mission, savings between 19 and 59 percent were obtained depending upon launch date.

Braun, Robert D.↗