Engineering topics

Christopher K Materese

Publications and source records attributed to Christopher K Materese.

9 records

NASA NTRS2024

Simplified Meteorite Parent Body Alteration of Amino Acids By Hydrothermal Processes

Amino acids have been identified in extraterrestrial materials such as meteorites and returned samples from asteroids and comets. Some of these amino acids or their precursors may have formed on icy interstellar dust grains or at a later phase when these grains became incorporated into larger parent bodies. In this work, we simulated parent body aqueous alteration of the residues from irradiated interstellar ice analogs in the presence of relevant minerals (pulverized serpentinite and Allende meteorite). We tracked the change in amino acid abundances as a function of hydrothermal processing time and examined how these differed based on the presence of minerals. We find that the presence of minerals and their mineralogy can have a significant impact on the formation and destruction of amino acids during simulated aqueous alteration experiments.

Christopher K Materese↗

NASA NTRS2022

Radiation-induced D/H Exchange Rate Constants in Aliphatics Embedded in Water Ice

Gas-phase and solid-state chemistry in low-temperature interstellar clouds and cores leads to a D/H enhancement in interstellar ices, which is eventually inherited by comets, meteorites, and even planetary satellites. Hence, the D/H ratio has been widely used as a tracer for the origins of extraterrestrial chemistry. However, the D/H ratio can also be influenced by cosmic rays, which are ubiquitous and can penetrate even dense interstellar molecular cores. The effects of such high-energy radiation on deuterium fractionation have not been studied in a quantitative manner. In this study, we present rate constants for radiation-induced D-to-H exchange for fully deuterated small (1–2 C) hydrocarbons embedded in H2O ice at 20 K and H-to-D exchange for the protiated forms of these molecules in D2O ice at 20 K. We observed larger rate constants for H-to-D exchange in the D2O ice versus D-to-H exchange in H2O ice, which we have attributed to the greater bond strength of C–D versus C–H. We find that the H-to-D exchange rate constants are smaller for protiated methane than ethane, in agreement with bond energies from the literature. We are unable to obtain rate constants for the unsaturated and reactive hydrocarbons ethylene and acetylene. Interpretation of the rate constants suggest that D/H exchange products are formed in abundance alongside radiolysis products. We discuss how our quantitative and qualitative data can be used to interpret the D/H ratios of aliphatic compounds observed throughout space.

Ice destruction↗

NASA NTRS2022

The Titan Haze Simulation (THS) Experiment on COSmIC. Part III. XANES Study of Laboratory Analogs of Titan Tholins

We have used the Titan Haze Simulation (THS) experimental set-up at NASA Ames’ COSmIC 19 facility to produce four laboratory analogs of Titan’s aerosols, or tholins. These tholin samples 20 were produced from four gas mixtures, representative of Titan’s atmosphere, of initial 21 compositions N2:CH4 (90:10 and 95:5) and N2:CH4:C2H2 (89.5:10:0.5 and 94.5:5:0.5) at 150 K, 22 using a plasma discharge in the stream of a jet-cooled gas expansion. Here we present an ex-situ 23 X-ray absorption near-edge structure (XANES) spectroscopy analysis of these four tholin 24 samples. The C- and N-XANES spectra show the presence of various functional groups 25 (aromatic carbon, imines, nitriles, etc.) whose abundances are correlated with (i) the relative 26 proportions between N2 and CH4, and (ii) the presence or absence of C2H2 in the initial mixtures. 27 In particular, mixtures containing C2H2 result in the formation of tholins consisting of more 28 aromatic structures and displaying larger relative amounts of imines and nitriles, but lower 29 overall nitrogen content. XANES spectroscopy also allowed for the determination of the 30 elemental C/N ratios for the four tholins, which were all found to be low (< 2.5) and consistent 31 with those measured for tholins produced in other, independent experimental set-ups. The C/N 32 ratios of tholins produced from gas mixtures that contained C2H2 (2.2–2.4) were found to be 33 about twice as large as those of tholins produced from gas mixtures that did not contain C2H234 (0.9–1.3). These new experimental results from the COSmIC/THS experiment demonstrate the 35 impact initial precursors have on the nitrogen chemistry during the formation of tholins, which 36 may help in the interpretation of observations and the development of models of Titan’s 37 atmosphere.

Titan↗

NASA NTRS2020

Laboratory Studies of Astronomical Ices: Reaction Chemistry and Spectroscopy

In this article, we will describe the work of the Cosmic Ice Laboratory at NASA’s Goddard Space Flight Center to characterize the composition of and to understand the chemistry occurring in icy bodies in the Solar System and beyond. Our work has touched on a wide range of extraterrestrial environments including icy interstellar grains, small bodies such as comets and asteroids, and planets and moons. We are especially interested in the chemical and physical changes that occur in ices as a result of thermal changes or exposure to radiation. To this end, we conduct experiments designed to simulate cold extraterrestrial environments and measure physical properties of single- and multi-component ices. We expose ices to radiation (e.g., MeV protons or keV-MeV electrons) or high-energy photons (e.g., UV) to initiate physical and chemical changes. We conduct experiments using cryo-vacuum chambers equipped with analytical tools and radiation sources to make most of our measurements, including the collection of all spectroscopic data,in situ. When possible and appropriate, we also collect reaction products for further ex situ analysis. The work of the Cosmic Ice Lab provides critical data to astrochemists and others seeking to understand observations, make predictions, and plan future space missions.

Christopher K Materese↗

NASA NTRS2020

The Radiation Stability of Thymine in Solid H2O

Nucleobases are of significant importance to all known organisms, may be an important building block of life, and could be important biosignatures of current or past life. Given their potential significance to the field of astrobiology, it is important to understand the survival of these molecules when subjected to ionizing radiation as is present in a range of extraterrestrial environments. In this work we present data on the kinetics of the radiolytic destruction of pure thymine, and water + thymine ice mixtures at temperatures from 13 to 150 K. Rate constants were measured using in situ infrared spectroscopy and radiolytic half-lives for thymine were computed for different planetary and interstellar environments. Our results demonstrate that the survival of thymine decreases as the dilution of thymine in water increases. Additionally, we find that thymine survival increases with ice temperature and that this decrease may be related to structure of the ice matrix.

nucleobases, radiolysis, astrobiology↗

NASA NTRS2019

Outgassing From the OSIRIS-REx Sample Return Capsule: Characterization and Mitigation

The Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer (OSIRIS-REx) spacecraft launched on September 8, 2016, beginning a seven-year journey to return at least 60 g of asteroid material from (101955) Bennu to Earth. During the outbound cruise, Doppler tracking of the spacecraft observed a small but measurable acceleration when the sample return capsule (SRC) was first placed in sunlight. Subsequent analysis determined that outgassing from the SRC is the most likely cause for the acceleration. This outgassing received combined engineering and scientific attention because it has potential implications both for spacecraft navigation performance and for contamination of the collected samples. Thermal modeling, laboratory studies of SRC materials, and monitoring of the acceleration are all consistent with H2O as the main component of the outgassing. Dedicated, in-flight campaigns continued to expose the SRC to sunlight until the acceleration dropped to the acceleration noise floor. Any residual amounts of H2O outgassing are not considered to be a hazard with regards to mission operations or pristine sample acquisition. The sample stow procedure has been updated to ensure that no direct line of site exists between any residual outgassing and the samples during future operations. Similar outgassing of the Stardust SRC probably also occurred. No adverse contamination of Stardust samples was observed that could be associated with this process. Future missions that use similar reentry vehicles should consider procedures to test for and, if necessary, mediate such outgassing after launch.

Origins, Spectral Interpretation, Resource Identif↗

NASA NTRS2019

Outgassing From the OSIRIS-REx Sample Return Capsule: Characterization and Mitigation

The Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer (OSIRIS-REx) spacecraft launched on September 8, 2016, beginning a seven-year journey to return at least 60 g of asteroid material from (101955) Bennu to Earth. During the outboundcruise, Doppler tracking of the spacecraft observed a small but measurable acceleration when the sample return capsule (SRC) was first placed in sunlight. Subsequent analysis determined that outgassing from the SRC is the most likely cause for the acceleration. This outgassing received combined engineering and scientific attention because it has potential implications both for spacecraft navigation performance and for contamination of the collected samples. Thermal modeling, laboratory studies of SRC materials, and monitoring of the acceleration are all consistent with H2O as the main component of the outgassing. Dedicated, in-flight campaigns continued to expose the SRC to sunlight until the acceleration dropped to the acceleration noise floor. Any residual amounts of H2O outgassing are not considered to be a hazard with regards to mission operations or pristine sample acquisition. The sample stow procedure has been updated to ensure that no direct line of site exists between any residual outgassing and the samples during future operations. Similar outgassing of the Stardust SRC probably also occurred. No adverse contamination of Stardust samples was observed that could be associated with this process. Future missions that use similar reentry vehicles should consider procedures to test for and, if necessary, mediate such outgassing after launch.

Scott A Sandford↗

NASA NTRS2018

The Photochemistry of Purine in Ice Analogs Relevant to Dense Interstellar Clouds

The aromatic nitrogen heterocyclic compound purine is the core structural framework of many important biomolecules, particularly nucleobases. Purine and purine derivatives have been observed in carbonaceous chondrites, and it has been hypothesized that the exogenous delivery of these compounds, along with many other biologically relevant compounds, may have played a role in the emergence of life. Numerous experiments in our laboratory have demonstrated that the nucleobases used by life to encode genetic material could have been produced abiotically under astrophysically relevant conditions. Specifically, the UV photoprocessing of pyrimidine and purine in simple ices of astrophysical interest has resulted in the production of all five biological nucleobases, namely, uracil (RNA), cytosine (RNA and DNA), thymine (DNA), adenine (RNA and DNA), and guanine (RNA and DNA). Additionally, follow-up work has examined the photochemistry of pyrimidine in more complex astrophysical ice mixtures to better understand the formation of these compounds under realistic conditions. In this work, we examine the photochemistry of purine in more complex ices of astrophysical interest and compare our results with those from simpler ice mixtures. We also examine the effects of competing parallel synthesis of organic compounds in the ices (unrelated to purine). Finally, we discuss the astrophysical and astrobiological implications of our findings.

Astrobiology↗

NASA NTRS2017

The Detection of 6.9 µm Emission Features in the Infrared Spectra of IRAS 04296+3429, IRAS 05341+0852, IRAS 22272+5435: Evidence for the Presence of Hn-PAHs in Post AGB Stars

Polycyclic aromatic hydrocarbons (PAHs) are generally believed to be ubiquitous in space and responsible for numerous telltale interstellar infrared emission bands. In Sandford et al., (2013), we suggested that polycyclic aromatic hydrocarbons with excess hydrogenation at their periphery (Hn-PAHs) may be an important subclass of these molecules in some astrophysical environments. These molecules are candidates to explain objects with anomalously large 3.4 μm features, which are presumed to be associated with the aliphatic C—H stretching vibrations of the excess hydrogen. In that work, we suggest that for Hn-PAHs to be a viable candidate as the source for this 3.4 μm feature, we must also expect to observe methylene scissoring modes at 6.9 μm. In this work, we continue to develop the Hn-PAH hypothesis with a focus on the 6.9 μm feature. We also present some new observations of three post-asymptotic giant branch (post- AGB) objects with abnormally large 3.4 μm features, IRAS 04296+3429, IRAS 05341+0852, IRAS 22272+5435, in addition to one post-AGB object with normal PAH emissions, IRAS 20000+3239. These observations were made using the FORCAST instrument in grism mode on the Stratospheric Observatory for Infrared Astronomy (SOFIA) aircraft (Adams et al. 2010) and demonstrate the presence of a 6.9 μm feature for the three objects with abnormally large 3.4 μm features and no detectable 6.9 μm feature for the normal PAH emitter. These results are consistent with the hypothesis that Hn-PAHs are a possible source of these infrared emission bands.

ISM↗