Engineering topics

Trainer, Melissa G.

Publications and source records attributed to Trainer, Melissa G..

12 records

NASA NTRS2018

Detection Opportunity for Aromatic Signature in Titan's Aerosols in the 4.1-5.3 μm Range

The Cassini/Huygens mission provided new insights on the chemistry of the upper atmosphere of Titan. The presence of large molecules and ions (>100's of amu) detected by Cassini at high altitude was not expected, and questions the original assumptions regarding the aerosol formation pathways. From recent laboratory studies, it has been shown that the inclusion of trace amounts of aromatic species drastically impacts the chemistry of aerosol formation and induces observable changes in the properties of the aerosols. In this Letter we focus on the effect of one of the simplest nitrogenous aromatics, pyridine (C5H5N), on the infrared signature of Titan's aerosol analogs. We introduce initial gas mixtures of (i) N2–C5H5N (100%/250 ppm), (ii) N2–CH4–C5H5N (99%/1%/250 ppm), and (iii) N2–CH4 (99%/1%) in a cold plasma discharge. The material produced, herein called tholins, is then analyzed by mid-infrared spectroscopy. When adding pyridine in the discharge, the tholins produced present an aromatic signature in the 4.1–5.3 μm (1850–2450 cm−1) spectral region, attributed to overtones of aromatic C–H out-of-plane bending vibrations. We also observe a spectral shift of the nitrile and iso-nitrile absorption band with the inclusion of pyridine in the gas mixture. These results could help to investigate the data obtained at Titan by the Cassini/Visual and Infrared Mapping Spectrometer (VIMS) instrument in the 1–5 μm infrared window.

Mathé, Christophe↗

NASA NTRS2017

Initial SAM Calibration Gas Experiments on Mars: Quadrupole Mass Spectrometer Results and Implications

The Sample Analysis at Mars (SAM) instrument suite of the Mars Science Laboratory (MSL) Curiosity rover is equipped to analyze both martian atmospheric gases and volatiles released by pyrolysis of solid surface materials, with target measurements including chemical and isotopic composition (Mahaffy et al., 2012). To facilitate assessment of instrument performance and validation of results obtained on Mars, SAM houses a calibration cell containing CO2, Ar, N2, Xe, and several fluorinated hydrocarbon compounds (Franz et al., 2014; Mahaffy et al., 2012). This report describes the first two experiments utilizing this calibration cell on Mars and gives results from analysis of data acquired with the SAM Quadrupole Mass Spectrometer (QMS). These data support the accuracy of isotope ratios obtained with the QMS (Conrad et al., 2016; Mahaffy et al., 2013) and provide ground-truth for reassessment of analytical constants required for atmospheric measurements, which were reported in previous contributions (Franz et al., 2015, 2014). The most significant implication of the QMS data involves reinterpretation of pre-launch contamination previously believed to affect only CO abundance measurements (Franz et al., 2015) to affect N2 abundances, as well. The corresponding adjustment to the N2 calibration constant presented here brings the atmospheric volume mixing ratios for Ar and N2 retrieved by SAM into closer agreement with those reported by the Viking mission (Owen et al., 1977; Oyama and Berdahl, 1977).

Sample Analysis at Mars Investigation↗

NASA NTRS2016

Environmental Temperature Effect on the Far-Infrared Absorption Features of Aromatic-Based Titan's Aerosol Analogs

Benzene detection has been reported in Titans atmosphere both in the stratosphere at ppb levels by remote sensing and in the thermosphere at ppm levels by the Cassini's Ion and Neutral Mass Spectrometer. This detection supports the idea that aromatic and heteroaromatic reaction pathways may play an important role in Titans atmospheric chemistry, especially in the formation of aerosols. Indeed, aromatic molecules are easily dissociated by ultraviolet radiation and can therefore contribute significantly to aerosol formation. It has been shown recently that aerosol analogs produced from a gas mixture containing a low concentration of aromatic and/or heteroaromatic molecules (benzene, naphthalene, pyridine, quinoline and isoquinoline) have spectral signatures below 500/cm, a first step towards reproducing the aerosol spectral features observed by Cassini's Composite InfraRed Spectrometer (CIRS) in the far infrared. In this work we investigate the influence of environmental temperature on the absorption spectra of such aerosol samples, simulating the temperature range to which aerosols, once formed, are exposed during their transport through Titans stratosphere. Our results show that environmental temperature does not have any major effect on the spectral shape of these aerosol analogs in the far-infrared, which is consistent with the CIRS observations.

Gautier, Thomas↗

NASA NTRS2016

Sample Handling and Instruments for the In-Situ Exploration of Ice-Rich Planets

NASA's key science goals for the exploration of the solar system seek a better understanding of the formation and evolutionary processes that have shaped planetary bodies and emphasize the search for habitable environments. Efforts are also made to detect and quantify resources that could be used for the support of human exploration. These themes call for chemistry and physical property observations that may be best approached by in situ measurements. NASA's planetary missions have progressively evolved from remote reconnaissance to in situ exploration with the ultimate goal to return samples. This chapter focuses on the techniques, available or in development, for advanced geophysical and chemical characterization of icy bodies, especially Mars polar areas, Enceladus, Titan, Europa, and Ceres. These astrobiological targets are the objects of recent or ongoing exploration whose findings are driving the formulation of new missions that involve in situ exploration. After reviewing the overall objectives of icy body exploration (Section 9.1) we describe key techniques used for addressing these objectives from surface platforms via geophysical observations (Section 9.2) and chemical measurements (Section 9.3).

planets↗

NASA NTRS2014

Titan Aerosol Analog Absorption Features Produced from Aromatics in the Far Infrared

We present results on the formation of Titan aerosol analogs produced via far-UV irradiation of five aromatic precursors: benzene, naphthalene, pyridine, quinoline and isoquinoline. This is the first reported evidence of far-IR emission features observed below 200 per cm in laboratory-created Titan aerosols. These laboratory studies were motivated by recent analyses of Cassini Composite Infrared Spectrometer (CIRS) spectra that show a broad aerosol emission feature in the far-IR spectral region centered near 140 per cm, which is unique to Titan's photochemically-produced aerosol. We find that all three of the aerosol analogs formed from nitrogen-containing aromatics have similar broad emission features near that of the observed CIRS far-IR aerosol spectral feature. In addition, the inclusion of 1.5% methane to that of trace amounts of benzene also gives rise to an aerosol with a weak far-IR emission feature located below 200 per cm.

atmosphere↗

NASA NTRS2014

Analytical Techniques for Retrieval of Atmospheric Composition with the Quadrupole Mass Spectrometer of the Sample Analysis at Mars Instrument Suite on Mars Science Laboratory

The Sample Analysis at Mars (SAM) instrument suite is the largest scientific payload on the Mars Science Laboratory (MSL) Curiosity rover, which landed in Mars׳ Gale Crater in August 2012. As a miniature geochemical laboratory, SAM is well-equipped to address multiple aspects of MSL׳s primary science goal, characterizing the potential past or present habitability of Gale Crater. Atmospheric measurements support this goal through compositional investigations relevant to martian climate evolution. SAM instruments include a quadrupole mass spectrometer, a tunable laser spectrometer, and a gas chromatograph that are used to analyze martian atmospheric gases as well as volatiles released by pyrolysis of solid surface materials (Mahaffy et al., 2012). This report presents analytical methods for retrieving the chemical and isotopic composition of Mars׳ atmosphere from measurements obtained with SAM׳s quadrupole mass spectrometer. It provides empirical calibration constants for computing volume mixing ratios of the most abundant atmospheric species and analytical functions to correct for instrument artifacts and to characterize measurement uncertainties. Finally, we discuss differences in volume mixing ratios of the martian atmosphere as determined by SAM (Mahaffy et al., 2013) and Viking (Owen et al., 1977, Oyama and Berdahl, 1977) from an analytical perspective. Although the focus of this paper is atmospheric observations, much of the material concerning corrections for instrumental effects also applies to reduction of data acquired with SAM from analysis of solid samples.

quadropole mass spectometer↗

NASA NTRS2012

Titan Aerosol Analogs from Aromatic Precursors: Comparisons to Cassini CIRS Observations in the Thermal Infrared

Since Cassini's arrival at Titan, ppm levels of benzene (C6H6) as well as large positive ions, which may be polycyclic aromatic hydrocarbons (PAHs). have been detected in the atmosphere. Aromatic molecules. photolytically active in the ultraviolet, may be important in the formation of the organic aerosol comprising the Titan haze layer even when present at low mixing ratios. Yet there have not been laboratory simulations exploring the impact of these molecules as precursors to Titan's organic aerosol. Observations of Titan by the Cassini Composite Infrared Spectrometer (CIRS) in the far-infrared (far-IR) between 560 and 20/cm (approx. 18 to 500 microns) and in the mid-infrared (mid-IR) between 1500 and 600/cm (approx. 7 to 17 microns) have been used to infer the vertical variations of Titan's aerosol from the surface to an altitude of 300 km in the far-IR and between 150 and 350 km in the mid-IR. Titan's aerosol has several observed emission features which cannot be reproduced using currently available optical constants from laboratory-generated Titan aerosol analogs, including a broad far-IR feature centered approximately at 140/cm (71 microns).

Trainer, Melissa G.↗

NASA NTRS2012

Influence of Benzene on the Optical Properties of Titan Haze Laboratory Analogs in the Mid-Visible

The Cassini Ion and Neutral Mass Spectrometer (Waite, Jr., et al., 2007) and the Composite Infrared Spectrometer (Coustenis, A., et al., 2007) have detected benzene in the upper atmosphere and stratosphere of Titan. Photochemical reactions involving benzene in Titan's atmosphere may influence polycyclic aromatic hydrocarbon formation, aerosol formation, and the radiative balance of Titan's atmosphere. We measure the effect of benzene on the optical properties of Titan analog particles in the laboratory. Using cavity ring-down aerosol extinction spectroscopy, we determine the real and imaginary refractive index at 532 nm of particles formed by benzene photolysis and Titan analog particles formed with ppm-levels of benzene. These studies are compared to the previous study by Hasenkopf, et a1. (2010) of Titan analog particles formed by methane photolysis.

Yoon, Y. Heidi↗

NASA NTRS2012

Nitrogen Incorporation in CH4-N2 Photochemical Aerosol Produced by Far UV Irradiation

Nitrile incorporation into Titan aerosol accompanying hydrocarbon chemistry is thought to be driven by extreme UV wavelengths (lambda < 120 nm) or magnetospheric electrons in the outer reaches of the atmosphere. Far UV radiation (120 - 200 nm), which is transmitted down to the stratosphere of Titan, is expected to affect hydrocarbon chemistry only and not initiate the formation of nitrogenated species. We have examined the chemical properties of photochemical aerosol produced at far UV wavelengths using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS), which allows for elemental analysis of particle-phase products. Our results show that aerosol formed from CH4/N2 photochemistry contains a surprising amount of nitrogen, up to 16% by mass, a result of photolysis in the far UV. The proportion of nitrogenated organics to hydrocarbon species is shown to be correlated with that of N2 in the irradiated gas. The aerosol mass greatly decreases when N2 is removed, indicating that N2 plays a major role in aerosol production. Because direct dissociation of N2 is highly improbable given the immeasurably low cross-section at the wavelengths studied, the chemical activation of N2 must occur via another pathway. Any chemical activation of N2 at wavelengths > 120 nm is presently unaccounted for in atmospheric photochemical models. We suggest that reaction with CH radicals produced from CH4 photolysis may provide a mechanism for incorporating N into the molecular structure of the aerosol. Further work is needed to understand the chemistry involved, as these processes may have significant implications for prebiotic chemistry on the early Earth and similar planets.

Trainer, Melissa G.↗

NASA NTRS2012

Atmospheric Prebiotic Chemistry and Organic Hazes

Earth's atmospheric composition at the time of the origin of life is not known, but it has often been suggested that chemical transformation of reactive species in the atmosphere was a significant source of pre biotic organic molecules. Experimental and theoretical studies over the past half century have shown that atmospheric synthesis can yield molecules such as amino acids and nucleobases, but these processes are very sensitive to gas composition and energy source. Abiotic synthesis of organic molecules is more productive in reduced atmospheres, yet the primitive Earth may not have been as reducing as earlier workers assumed, and recent research has reflected this shift in thinking. This work provides a survey of the range of chemical products that can be produced given a set of atmospheric conditions, with a particular focus on recent reports. Intertwined with the discussion of atmospheric synthesis is the consideration of an organic haze layer, which has been suggested as a possible ultraviolet shield on the anoxic early Earth. Since such a haze layer - if formed - would serve as a reservoir for organic molecules, the chemical composition of the aerosol should be closely examined. The results highlighted here show that a variety of products can be formed in mildly reducing or even neutral atmospheres, demonstrating that contributions of atmospheric synthesis to the organic inventory on early Earth should not be discounted. This review intends to bridge current knowledge of the range of possible atmospheric conditions in the prebiotic environment and pathways for synthesis under such conditions by examining the possible products of organic chemistry in the early atmosphere.

Trainer, Melissa G.↗

NASA NTRS2011

Aromatic Structure in Simulates Titan Aerosol

Observations of Titan by the Cassini Composite Infrared Spectrometer (CIRS) between 560 and 20 per centimeter (approximately 18 to 500 micrometers) have been used to infer the vertical variations of Titan's ice abundances, as well as those of the aerosol from the surface to an altitude of 300 km [1]. The aerosol has a broad emission feature centered approximately at 140 per centimeter (71 micrometers). As seen in Figure 1, this feature cannot be reproduced using currently available optical constants from laboratory-generated Titan aerosol analogs [2]. The far-IR is uniquely qualified for investigating low-energy vibrational motions within the lattice structures of COITIDlex aerosol. The feature observed by CIRS is broad, and does not likely arise from individual molecules, but rather is representative of the skeletal movements of macromolecules. Since Cassini's arrival at Titan, benzene (C6H6) has been detected in the atmosphere at ppm levels as well as ions that may be polycyclic aromatic hydrocarbons (PAHs) [3]. We speculate that the feature may be a blended composite that can be identified with low-energy vibrations of two-dimensional lattice structures of large molecules, such as PAHs or nitrogenated aromatics. Such structures do not dominate the composition of analog materials generated from CH4 and N2 irradiation. We are performing studies forming aerosol analog via UV irradiation of aromatic precursors - specifically C6H6 - to understand how the unique chemical architecture of the products will influence the observable aerosol characteristics. The optical and chemical properties of the aromatic analog will be compared to those formed from CH4/N2 mixtures, with a focus on the as-yet unidentified far-IR absorbance feature. Preliminary results indicate that the photochemically-formed aromatic aerosol has distinct chemical composition, and may incorporate nitrogen either into the ring structure or adjoined chemical groups. These compositional differences are demonstrated in the aerosol mass spectra shown in Figure 2. The aromatic aerosol also demonstrates strong chemical reactivity when exposed to laboratory air, indicating substantial stored chemical potential. Oxidatoin and solubility studies wil be presented and implicatoins for prebiotic chemistry o nTitan will be discussed.

Trainer, Melissa G.↗

NASA NTRS2010

The Formation of Sulfate and Elemental Sulfur Aerosols Under Varying Laboratory Conditions: Implications for Early Earth

The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45 x 10(exp 9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO2) by UV light with lambda < 220 nm has been shown in models and some initial laboratory studies to create a S-MIF; however, sulfur must leave the atmosphere in at least two chemically different forms to preserve any S-MIF signature. Two commonly cited examples of chemically different sulfur species that could have exited the atmosphere are elemental sulfur (S8) and sulfuric acid (H2S04) aerosols. Here, we use real-time aerosol mass spectrometry to directly detect the sulfur-containing aerosols formed when SO2 either photolyzes at wavelengths from 115 to 400 nm, to simulate the UV solar spectrum, or interacts with high-energy electrons, to simulate lightning. We found that sulfur-containing aerosols form under all laboratory conditions. Further, the addition of a reducing gas, in our experiments hydrogen (H2) or methane (CH4), increased the formation of S8. With UV photolysis, formation of S8 aerosols is highly dependent on the initial SO2 pressure; and S8 is only formed at a 2% SO2 mixing ratio and greater in the absence of a reductant, and at a 0.2% SO2 mixing ratio and greater in the presence of 1000 ppmv CH4. We also found that organosulfur compounds are formed from the photolysis of CH4 and moderate amounts of SO2, The implications for sulfur aerosols on early Earth are discussed.

DeWitt, H. Langley↗