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At least 145 records · Page 8

Investigating the Chemical Pathways to PAH- and PANH-Based Aerosols in Titan's Atmospheric chemistry

A complex organic chemistry between Titan's two main constituents, N2 and CH4, leads to the production of more complex molecules and subsequently to solid organic aerosols. These aerosols are at the origin of the haze layers giving Titan its characteristic orange color. In situ measurements by the Ion Neutral Mass Spectrometer (INMS) and Cassini Plasma Spectrometer (CAPS) instruments onboard Cassini have revealed the presence of large amounts of neutral, positively and negatively charged heavy molecules in the ionosphere of Titan. In particular, benzene (C6H6) and toluene (C6H5CH3), which are critical precursors of polycyclic aromatic hydrocarbon (PAH) compounds, have been detected, suggesting that PAHs might play a role in the production of Titan s aerosols. Moreover, results from numerical models as well as laboratory simulations of Titan s atmospheric chemistry are also suggesting chemical pathways that link the simple precursor molecules resulting from the first steps of the N2-CH4 chemistry (C2H2, C2H4, HCN ...) to benzene, and to PAHs and nitrogen-containing PAHs (or PANHs) as precursors to the production of solid aerosols.

Sciamma-O'Brien, Ella Marion↗

A Near-Infrared and Thermal Imager for Mapping Titan's Surface Features

Approximately 10% of the solar insolation reaches the surface of Titan through atmospheric spectral windows. We will discuss a filter based imaging system for a future Titan orbiter that will exploit these windows mapping surface features, cloud regions, polar storms. In the near-infrared (NIR), two filters (1.28 micrometer and 1.6 micrometer), strategically positioned between CH1 absorption bands, and InSb linear array pixels will explore the solar reflected radiation. We propose to map the mid, infrared (MIR) region with two filters: 9.76 micrometer and 5.88-to-6.06 micrometers with MCT linear arrays. The first will map MIR thermal emission variations due to surface albedo differences in the atmospheric window between gas phase CH3D and C2H4 opacity sources. The latter spans the crossover spectral region where observed radiation transitions from being dominated by thermal emission to solar reflected light component. The passively cooled linear arrays will be incorporated into the focal plane of a light-weight thin film stretched membrane 10 cm telescope. A rad-hard ASIC together with an FPGA will be used for detector pixel readout and detector linear array selection depending on if the field-of-view (FOV) is looking at the day- or night-side of Titan. The instantaneous FOV corresponds to 3.1, 15.6, and 31.2 mrad for the 1, 5, and 10 micrometer channels, respectively. For a 1500 km orbit, a 5 micrometer channel pixel represents a spatial resolution of 91 m, with a FOV that spans 23 kilometers, and Titan is mapped in a push-broom manner as determined by the orbital path. The system mass and power requirements are estimated to be 6 kg and 5 W, respectively. The package is proposed for a polar orbiter with a lifetime matching two Saturn seasons.

Aslam, S.↗

The Evolution of Hydrocarbons in Saturn's Northern Storm Region

The massive storm at 40N on Saturn that began in December 2010 has produced significant and lasting effects in the northern hemisphere on temperature and species abundances (Fletcher et aL 2011). The northern storm region was observed on several occasions between March 2011 and April 2012 by Cassini's Composite Infrared Spectrometer (CIRS) at a spectral resolution (0.5/cm) which permits the study of trace species in Saturn's stratosphere. During this time period, stratospheric temperatures in regions referred to as "beacons" (warm regions at specific longitudes at the latitude of the storm) became significantly warmer than pre-storm values of 140K, peaking near 220K, and subsequently cooling. These warm temperatures led to greatly enhanced infrared emission due to C4H2, C3H4, C2H2, and C2H6 in the stratosphere as well as the first detection of C2H4 on Saturn in the thermal infrared (Hesman et al. 2012). Using CH4 as a thermometer of Saturn's stratosphere in the beacon regions, we can derive the mixing ratios of each of these molecules. The most common hydrocarbons (C2H2 and C2H6) serve as dynamical tracers on Saturn and their abundances may constrain vertical motion in the stratosphere. All of these hydrocarbons are products of methane photolysis. Since many of the photochemical reactions that produce heavier hydrocarbons such as C4H2 and C3H4 are temperature sensitive, the beacon region provides a natural laboratory for studying these reactions on Saturn. We will discuss the time evolution of the abundances of each of these hydrocarbons from their pre-storm values, through the period of maximum heating , and during the period of cooling that is taking place in Saturn's stratosphere.

Bjoraker, Gordon↗

Elusive Ethylene Detected in Saturns Northern Storm Region

The massive eruption at 40 deg. N (planetographic latitude) on Saturn in 2010 December has produced significant and lasting effects in the northern hemisphere on temperature and species abundances. The northern storm region was observed on many occasions in 2011 by Cassini's Composite Infrared Spectrometer (CIRS). In 2011 May, temperatures in the stratosphere greater than 200 K were derived from CIRS spectra in the regions referred to as "beacons" (warm regions in the stratosphere). Ethylene has been detected in the beacon region in Saturn's northern storm region using CIRS. Ground-based observations using the high-resolution spectrometer Celeste on the McMath-Pierce Telescope on 2011 May 15 were used to confirm the detection and improve the altitude resolution in the retrieved profile. The derived ethylene profile from the CIRS data gives a C2H4 mole fraction of 5.9 +/- 4.5 x 10(exp -7) at 0.5 mbar, and from Celeste data it gives 2.7 +/- 0.45 x 10(exp -6) at 0.1 mbar. This is two orders of magnitude higher than the amount measured in the ultraviolet at other latitudes prior to the storm. It is also much higher than predicted by photochemical models, indicating that perhaps another production mechanism is required or a loss mechanism is being inhibited.

Hesman, B. E.↗

Investigating Titan's Atmospheric Chemistry at Low Temperature in Support of the NASA Cassini Mission

Titan's atmosphere, composed mainly of N2 and CH4, is the siege of a complex chemistry induced by solar UV radiation and electron bombardment from Saturn's magnetosphere. This organic chemistry occurs at temperatures lower than 200 K and leads to the production of heavy molecules and subsequently solid aerosols that form the orange haze surrounding Titan. The Titan Haze Simulation (THS) experiment has been developed on the COSMIC simulation chamber at NASA Ames in order to study the different steps of Titan's atmospheric chemistry at low temperature and to provide laboratory data in support for Cassini data analysis. The chemistry is simulated by plasma in the stream of a supersonic expansion. With this unique design, the gas mixture is adiabatically cooled to Titan-like temperature (approx. 150 K) before inducing the chemistry by plasma discharge. Different gas mixtures containing N2, CH4, and the first products of the N2,-CH4 chemistry (C2H2, C2H4, C6H6...) but also heavier molecules such as PAHs or nitrogen containing PAHs can be injected. Both the gas phase and solid phase products resulting from the plasma-induced chemistry can be monitored and analyzed. Here we present the results of recent gas phase and solid phase studies that highlight the chemical growth evolution when injecting heavier hydrocarbon trace elements in the initial N2-CH4 mixture. Due to the short residence time of the gas in the plasma discharge, only the first steps of the chemistry have time to occur in a N2-CH4 discharge. However by adding acetylene and benzene to the initial N2-CH4 mixture, we can study the intermediate steps of Titan's atmospheric chemistry as well as specific chemical pathways. These results show the uniqueness of the THS experiment to help understand the first and intermediate steps of Titan fs atmospheric chemistry as well as specific chemical pathways leading to Titan fs haze formation.

Sciamma-O'Brien, Ella↗

Infrared Spectra and Optical Constants of Astronomical Ices: II. Ethane and Ethylene

Infrared spectroscopic observations have established the presence of hydrocarbon ices on Pluto and other TNOs, but the abundances of such molecules cannot be deduced without accurate optical constants (n, k) and reference spectra. In this paper we present our recent measurements of near- and mid-infrared optical constants for ethane (C2H6) and ethylene (C2H4) in multiple ice phases and at multiple temperatures. As in our recent work on acetylene (C2H2), we also report new measurements of the index of refraction of each ice at 670 nm. Comparisons are made to earlier work where possible, and electronic versions of our new results are made available.

Ices↗

Radiation Chemistry of Solid Acetone in the Interstellar Medium - A New Dimension to an Old Problem

A laboratory investigation of acetone, an interstellar and cometary molecule, has produced new results concerning its decomposition in a radiation environment. Mid-infrared spectroscopy has been used to follow amorphous acetone's destruction by ionizing radiation (1 MeV protons) at 20 K. Radiation products identified are the CH4, CO, and CO2 usually made in such experiments, along with ketene, allene, and the acetonyl radical, all identified here for the first time in irradiated solid acetone. Evidence for the reduction product 2-propanol was suggestive, but a firm identification could not be made either for it or for the C2 hydrocarbons (i.e., C2H6, C2H4, C2H2). The acetyl radical was not observed as a radiation product. Isotopically labeled reagents were used to demonstrate ketene formation and to emphasize that multiple approaches are needed for robust assignments of infrared spectral features of irradiated icy solids. Results from a supporting radiation experiment with isotopically labeled acetic acid are described. Comparisons are made to a previous study of acetone's stability in extraterrestrial radiation environments, and caution is urged in measuring and interpreting CO abundances in irradiated icy solids.

cometary molecule↗

Radiation Chemistry of Solid Acetone in the Interstellar Medium - A New Dimension to an Old Problem

A laboratory investigation of acetone, an interstellar and cometary molecule, has produced new results concerning its decomposition in a radiation environment. Mid-infrared spectroscopy has been used to follow amorphous acetone’s destruction by ionizing radiation (1 MeV protons) at 20 K. Radiation products identified are the CH4, CO, and CO2 usually made in such experiments, along with ketene, allene, and the acetonyl radical, all identified here for the first time in irradiated solid acetone. Evidence for the reduction product 2-propanol was suggestive, but a firm identification could not be made either for it or for the C2 hydrocarbons (i.e., C2H6, C2H4, C2H2). The acetyl radical was not observed as a radiation product. Isotopically labeled reagents were used to demonstrate ketene formation and to emphasize that multiple approaches are needed for robust assignments of infrared spectral features of irradiated icy solids. Results from a supporting radiation experiment with isotopically labeled acetic acid are described. Comparisons are made to a previous study of acetone’s stability in extraterrestrial radiation environments, and caution is urged in measuring and interpreting CO abundances in irradiated icy solids.

R. L. Hudson↗

Decomposition of Electron Ionization Mass Spectra for Space Application Using a Monte-Carlo approach

Rationale: Quadrupole mass spectrometers equipped with an electron ionization (EI) sources have been widely used in space exploration to investigate the composition of planetary surfaces and atmospheres. However, the complexity of the samples and the minimal calibration for the fragmentation of molecules in the ionization chambers have prevented the deconvolution of the majority of the mass spectra obtained at different targets, thus limiting the determination of the exact composition of the samples analyzed. We propose a Monte‐Carlo approach to solve this issue mathematically. Methods: We decomposed simulated mass spectra of mixtures acquired with unit resolving power mass spectrometers and EI sources into the sum of the single components fragmentation patterns weighted by their relative concentration using interior‐point least‐square fitting. To fit compounds with poorly known fragmentation patterns, we used a Monte‐Carlo method to vary the intensity of individual fragment ions. We then decomposed the spectrum thousands of times to obtain a statistical distribution. Results: By performing the deconvolution on a mixture of seven different molecules with interfering fragmentation patterns (H2O, O2, CH4, Ar, N2, C2H4, and C2H6) we show that this approach retrieves the mixing ratio of the individual components more accurately than regular mass spectra decomposition methods that rely on fragmentation patterns from general databases. It also provides the probability density function for each species's mixing ratio. Conclusions: By removing the solution degeneracy in the decomposition of mass spectra, the method described herein could significantly increase the scientific retrieval from archived space flight mass spectrometry data, where calibration of the ionization source is no longer an option.

Thomas Gautier↗

Comprehensive Investigation of Mars Methane and Organics with ExoMars/NOMAD

Methane (CH4) on Mars has attracted a great deal of attention since it was first detected in January 2003. As methane is considered a potential marker for past/present biological or geological activity, any possible detection would require evidence with strong statistical significance. Ethane (C2H6) and ethylene (C2H4) are also relevant chemical species as their shorter lifetimes in the Martian atmosphere make them excellent tracers for recent and ongoing releases. If detected, a CH4/C2Hn ratio could aid in constraining the potential source of organic production. Here we present the results of an extensive search for hydrocarbons in the Martian atmosphere in 240,000 solar occultation measurements performed by the ExoMars Trace Gas Orbiter/NOMAD instrument from April 2018 to April 2019. The observations are global, covering all longitudes and latitudes from 85°N to 85°S, and sampled from 6-100 km altitude with a typical vertical resolution of 2km. There were no statistically significant detections of organics and new stringent upper limits for global ethane and ethylene were set at 0.1 ppbv and 130.7 ppbv, respectively. No global background level of methane was observed, obtaining an upper limit of 0.06 ppbv, in agreement with early results from ExoMars (Korablev et al., 2019). Dedicated searches for localized plumes at more than 2000 locations provided no positive detections, implying that if methane were released in strong and rapid events, the process would have to be sporadic.

Elise W Knutsen↗

Preliminary XANES Analysis of Laboratory Analogs of Titan Tholins

Titan, the largest moon of Saturn, is a fascinating object. It is the only other object in the Solar System, besides Earth, with a dense (1.5 bar at the surface) atmosphere whose composition is dominated by N2, with CH4 as the second most abundant gas. A complex organic chemistry between N2 and CH4, induced by solar UV photons and energetic particles, results in the formation of a large variety of organic compounds, including hydrocarbons (e.g., C2H2, C2H4, C2H6, C3H4, C6H6), nitriles (e.g., HCN, HNC, HC3N, CH3CN, C2N2), as well as larger molecules that include aromatic and heteroaromatic compounds [1]. This complex organic chemistry also leads to the formation of aerosols that play an important role in Titan’s atmospheric dynamics, climate, as well as surface composition and processes. Because of its N2-based dense atmosphere, and its CH4 cycle that resembles the hydrological cycle on Earth, Titan is often considered to be an analog of early Earth. In recent years, Titan’s atmosphere and surface were monitored in detail by the NASA Cassini mission, which orbited the Saturnian system from 2004 to 2017, as well as the ESA Huygens probe, which plunged into Titan’s atmosphere and landed on its surface in 2005.

Titan↗

Development of Electrolytic Oxygen Recovery System for Advanced Life Support

The oxygen (O2) recovery system for the International Space Station (ISS) can recover approximately 50 percent of O2 from metabolic carbon dioxide (CO2). Increasing the O2 recovery rate and closing the open loop for future long duration crewed missions in space beyond Low Earth Orbit (LEO) is essential. There are several developmental efforts underway to increase the recovery rate. However, most of these technologies result in a complex, heavy, and power consuming system. The desired exploration O2 recovery system would be reliable and efficient with maximum O2 recovery. Marshall Space Flight Center (MSFC) is currently investigating an electrolytic O2 recovery approach that will increase the O2 recovery to greater than 70 percent as well as lowering the complexity, mass, and power consumption than most other technologies currently under development. The electrolytic O2 recovery system consists of a Microfluidic Electrochemical Reactor (MFECR) that is based on the electrochemical reduction of CO2 to O2 and ethylene (C2H4) using water (H2O) as precursor and operates at standard condition with a theoretical recovery rate of 73 percent. In 2016, NASA’s Game Changing Development Program awarded the University of Texas Arlington (UTA) a grant to initiate the development of the MFECR. Since 2019, MSFC and UTA have been collaborating with the current goals of increasing the O2 recovery efficiency, advancing the technology readiness to a Technology Readiness Level (TRL) 4, and maturing the system to process CO2 of one crew-member. Based on the results from UTA’s initial efforts, the following were identified as key areas of improvement in order to maximize O2 recovery for the system: further development of the anode material and cathode catalyst, model-based cell design optimization, and the addition of a separation system and fuel cell. This paper will present the current developmental efforts of the electrolytic system including MFECR design and overall system enhancements as well as results from single cell stack testing.

Brittany R Brown↗

Compositional Analysis of Titan’s Atmosphere Using Spitzer Infrared Spectrograph Data

We present, for the first time, infrared spectra from the Spitzer Space Telescope’s Infrared Spectrograph (IRS) (2004-2008) of Titan in both the short wavelength-low resolution(SL, R=60~127,5.13-14.29 μm) and short wavelength-high resolution channels (SH, R=600, 9.89-19.51 μm) showing the emissions of CH4, C2H4, C2H2, C2H6, HCN, CO2, HC3N, C3H4, C4H2, and C3H8. Spitzer IRS data has been used to measure atmospheric composition of various Solar System bodies, including Neptune [1] and Uranus [2],[3]. Although Spitzer took multiple dedicated observations of Titan, none of the results have been modeled before. We conduct our own investigation of these datasets and search for new results. We retrieve temperature and gas composition profiles and compare the results obtained for Titan to those of the Cassini Composite Infrared Spectrometer (CIRS) and the Infrared Space Observatory Short Wavelength Spectrometer [4], and comment on the effect of spectral resolution on retrieved information content. We conclude by recommending gaps in current spectroscopic knowledge of molecular bands that could be addressed by theoretical and laboratory study to aid future astronomical studies of Titan, for example the James Webb Space Telescope (JWST) and the Stratospheric Observatory for Infrared Astronomy (SOFIA) Acknowledgments: Data analyzed in this project is public available online on the Spitzer Heritage Archive (sha.ipac.caltech.edu). This research has made use of the NASA/IPAC Infrared Science Archive, which is funded by the National Aeronautics and Space Administration and operated by the California Institute of Technology.

Titan↗

Plasma Assisted Trash Conversion with CO2 Carrier Gas

A sub-atmospheric plasma solid-to-gas conversion system operating under 500 W was tested to be viable for waste conversion to a gaseous state without the use of a feedstock gas as shown in previous plasma torch works. This manuscript lays the groundwork into the feasibility of low-pressure solid-to-gas conversion, reaction chemistry of the by-product gases, and power consumption. The results have shown the possibility of gasification at reduced pressures without the consumable use of a feedstock carrier gas in previous studies. Thus far, the percent gasification averaged around 36% in pre-pellet trials, with the system being far from optimized. The products include H2, CO2, CO, C2H4, and C2H6. Hydrogen production was higher as expected in a CO2-like environment once the gasification process begins. The energy required to generate the plasma was on the order of that previously reported at atmospheric pressures. The ability to eliminate the need for any consumables that were required in previous iterations greatly improves the cost and operational logistics of plasma gasification equipment. Although further development of the system is needed for increased gasification percentages, elimination of useable commodities greatly favors such a system for trash management beyond low Earth orbit.

Malay Shah↗

Volatile Abundances, Extended Coma Sources, and Nucleus Ice Associations in Comet C/2014 Q2 (Lovejoy)

High-resolution infrared spectra of comet C/2014 Q2 Lovejoy were acquired with NIRSPEC at the W. M. Keck Observatory on two post-perihelion dates(UT 2015 February 2 and 3).H2O was measured simultaneously with CO,CH3OH, H2CO, CH4, C2H6,C2H4, C2H2, HCN, and NH3 on both dates, and rotational temperatures, production rates, relative abundances, H2O ortho-to-para ratios, and spatial distributions in the coma were determined. The first detection of C2H4in a comet from ground-based observations is reported. Abundances relative to H2O for all species were found to be in the typical range compared with values for other comets in the overall population to date. There is evidence of variability in rotational temperatures and production rates on timescales that are small compared with the rotational period of the comet. Spatial distributions of volatiles in the coma suggest complex outgassing behavior.CH3OH, HCN, C2H6, and CH4 spatial distributions in the coma are consistent with direct release from associated ices in the nucleus and are peaked in a more sunward direction compared with co-measured dust. H2O spatial profiles are clearly distinct from these other four species, likely due to a sizable coma contribution from icy grain sublimation.Spatial distributions for C2H2,H2CO, and NH3suggest substantial contributions from extended coma sources, providing further evidence for distinct origins and associations for these species in comets. CO shows a different spatial distribution compared with other volatiles, consistent with jet activity from discrete nucleus ice sources.

Neil Dello Russo↗

Tunable Laser Spectrometers for Planetary Science

Distinguishing planetary formation and evolution pathways and understanding the origins of volatiles on planetary bodies requires determination of relative abundances and isotope ratios in the noble gases, and also of the isotope ratios in C, H, N, O and S at high precisions. Traditional planetary mass spectrometers uniquely provide excellent survey capability including the noble gas relative abundances and their isotope ratios. However, to distinguish planetary evolution models for the outer planets, stable isotope ratios in C and O require precisions of ∼10 or better, readily achievable with a tunable laser spectrometer (TLS). As demonstrated on the Mars Curiosity rover, and as planned for a now-selected NASA Venus mission, tunable laser spectrometers play a unique role synergistic with the capabilities of planetary mass spectrometers. The TLS technique of recording infrared absorption spectra at ultrahigh resolution (resolving power λ/δλ ∼ 5 million) provides unambiguous detection of a wide variety of gases such as H2O, H2O2, H2CO, HOCl, NO, NO2, HNO3, N2O, O3, CO, CO2, NH3, N2H4, PH3, H2S, SO2, OCS, HCl, HF, O2, HCN, and CH4, C2H2, C2H4, C2H6 at parts-per-billion levels. Through line-depth or line-area ratio comparisons of adjacent spectral lines, planetary TLS instruments can achieve isotope ratio measurements in C, H, N, O, and S molecules at precisions of ∼1–2, including for the triple isotope components of O and S. Expected performance of TLS instruments for Venus, Saturn, Enceladus and Uranus will be described as constrained by actual measurements reported at Mars on the Curiosity rover.

Planetary↗

Switching CO 2 Electroreduction Selectivity Between C 1 and C 2 Hydrocarbons on Cu Gas-Diffusion Electrodes

We report that regulating the selectivity toward a target hydrocarbon product is still the focus of CO 2 electroreduction. Here, we discover that the original surface Cu species in Cu gas-diffusion electrodes plays a more important role than the surface roughness, local pH, and facet in governing the selectivity toward C 1 or C 2 hydrocarbons. The selectivity toward C 2 H 4 progressively increases, while CH 4 decreases steadily upon lowering the Cu oxidation species fraction. At a relatively low electrodeposition voltage of 1.5 V, the Cu gas-diffusion electrode with the highest Cu δ+ /Cu 0 ratio favors the pathways of hydrogenation to form CH 4 with maximum Faradaic efficiency of 65.4% and partial current density of 228 mA cm -2 at -0.83 V vs RHE. At 2.0 V, the Cu gas-diffusion electrode with the lowest Cu δ+ /Cu 0 ratio prefers C–C coupling to form C 2+ products with Faradaic efficiency topping 80.1% at -0.75 V vs RHE, where the Faradaic efficiency of C 2 H 4 accounts for 46.4% and the partial current density of C 2 H 4 achieves 279 mA cm -2 . This work demonstrates that the selectivity from CH 4 to C 2 H 4 is switchable by tuning surface Cu species composition of Cu gas-diffusion electrodes.

36 MATERIALS SCIENCE↗

Cooperative and bifunctional Ga-Ca-Cr 2 O 3 @CaO structured monoliths as versatile platform for reactive capture of CO 2 and its subsequent conversion to ethylene

Cooperative and bifunctional materials (BFMs) that integrate adsorbents and catalysts offer a promising strategy for the reactive capture of CO 2 to produce valuable fuels and chemicals. In this study, we developed structured BFMs via 3D printing that combine CaO as an adsorbent with Ga–Ca–Cr 2 O 3 metal oxides as the catalyst for the reactive capture of CO 2 and its subsequent conversion to C 2 H 4 via the oxidative dehydrogenation of C 2 H 6 (CO 2 -ODHE). Three different Ga–Ca compositions were used to modify the catalyst surface characteristics and enhance C 2 H 4 selectivity. In these formulations, Ga ions stabilize the oxygen lattice of the BFM, while Ca ions interact strongly with Cr to form CaCrO 4 , thereby altering the oxygen species and enhancing the material’s basic properties. Under adsorption–reaction conditions at 600–650 °C, the optimal BFM achieved an excellent C 2 H 4 selectivity of 96.4 %, attributed to a balanced redox process and improved basicity that facilitate efficient C 2 H 6 conversion and rapid desorption of C 2 H 4 without excessive oxidation. Overall, this work provides new insights into the formulation of BFMs monoliths and highlights the critical role of catalytic surface modification in enhancing C 2 H 4 selectivity in the CO 2 -ODHE reactive capture process.

C2H4 production↗