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NASA NTRS2020

Incorporation of Nitrogen into Organics Produced by Fischer-Tropsch Type Chemistry

Laboratory simulations have demonstrated that hydrothermal systems have the potential to produce a range of organic compounds through Fischer-Tropsch type (FTT) chemistry. The distribution of products depends on several factors, including the abundance and composition of feed-stock molecules, reaction temperature, and the physical and chemical characteristics of catalytic materials included in the reactions. The majority of studies per-formed to date have focused solely on inclusion of CO2 or CO and H2 as the carbon, oxygen and hydrogen sources, which limits the possible products to hydro-carbons, alcohols and carboxylic acids. A few studies have included nitrogen in the form of ammonia, which led to the production of amino acids and nitrogenous bases; and a separate suite of studies included sulfur as sulfide minerals or H2S, which yielded products such as thiols and amino acids. Although these demonstrations provide compelling evidence that FTT reactions can produce compounds of interest for the origins of life, such reactions have been conducted under a very limited range of conditions and the synthetic reaction mechanisms have generally not been well-characterized. As a consequence, it is difficult to extrapolate these results to geologic systems or to evaluate how variations in reactant compositions would affect the distribution of products over time. We have begun a series of laboratory experiments that will incorporate a range of precursor molecules in varying compositions to determine how these variables affect the relative amounts and speciation of life-essential elements in organic molecules produced under FTT conditions. In the present work, we focus on systems containing C, H, O and N.

Burton, A. S.↗
NASA NTRS2018

Impact-Seismic Investigations of the InSight Mission

Impact investigations will be an important aspect of the InSight mission. One of the scientific goals of the mission is a measurement of the current impact rate at Mars. Impacts will additionally inform the major goal of investigating the interior structure of Mars. In this paper, we review the current state of knowledge about seismic signals from impacts on the Earth, Moon, and laboratory experiments. We describe the generalized physical models that can be used to explain these signals. A discussion of the appropriate source time function for impacts is presented, along with spectral characteristics including the cutoff frequency and its dependence on impact momentum. Estimates of the seismic efficiency (ratio between seismic and impact energies) vary widely. Our preferred value for the seismic efficiency at Mars is 5 × 10−4, which we recommend using until we can measure it during the InSight mission, when seismic moments are not used directly. Effects of the material properties at the impact point and at the seismometer location are considered. We also discuss the processes by which airbursts and acoustic waves emanate from bolides, and the feasibility of detecting such signals. We then consider the case of impacts on Mars. A review is given of the current knowledge of present-day cratering on Mars: the current impact rate, characteristics of those impactors such as velocity and directions, and the morphologies of the craters those impactors create. Several methods of scaling crater size to impact energy are presented. The Martian atmosphere, although thin, will cause fragmentation of impactors, with implications for the resulting seismic signals. We also benchmark several different seismic modeling codes to be used in analysis of impact detections, and those codes are used to explore the seismic amplitude of impactinduced signals as a function of distance from the impact site. We predict a measurement of the current impact flux will be possible within the timeframe of the prime mission (one Mars year) with the detection of ∼ a few to several tens of impacts. However, the error bars on these predictions are large. Specific to the InSight mission, we list discriminators of seismic signals from impacts that will be used to distinguish them from marsquakes. We describe the role of the InSight Impacts Science Theme Group during mission operations, including a plan for possible night-time meteor imaging. The impacts detected by these methods during the InSight mission will be used to improve interior structure models, measure the seismic efficiency, and calculate the size frequency distribution of current impacts.

Ingrid Daubar↗
NASA NTRSDate not supplied

Computing rovibrational, vibrational, and cascade emission spectra for comparison to astronomical observations

Over the last several years, our group has been involved in developing approaches to compute highly accurate spectroscopic constants and vibrational frequencies for small transient molecules that may be used in the interpretation and assignment of high-resolution laboratory experiments as well as high-resolution astronomical spectra. Additionally, we have used the computed spectroscopic constants to simulate purely rotational and rovibrational spectra so that these may be compared directly with high-resolution astronomical observations, and we have worked on developing approaches that can be applied to much larger molecules, such as polycyclic aromatic hydrocarbon (PAH) molecules, where we can explicitly determine anharmonic corrections to vibrational frequencies as well as take into account intensity sharing due to resonances. In addition, for PAH molecules we have used the anharmonic data to compute a library of temperature-dependent anharmonic vibrational spectra, with proper inclusion of polyad resonances, which can then be used to model the cascade emission spectra of PAH molecules – the type of spectra directly observed by astronomers. Another part of our work in spectroscopic signatures involves computing highly accurate line lists for common molecules, such as CO2, SO2, and NH3, which occur in many astrophysical environments, including the atmospheres of exoplanents, and often need to have their lines identified in high-resolution observations in order to determine which lines are due to other molecules. In order to characterize the atmospheres of hot exoplanets, these line lists need to be very accurate and extend to very high energies. I will discuss our latest work in these areas of astrochemical spectroscopy research.

Timothy J Lee↗
NASA NTRSDate not supplied

INCORPORATION OF NITROGEN INTO ORGANICS PRODUCED BY FISCHER-TROPSCH TYPE CHEMISTRY

Laboratory simulations have demonstrated that hydrothermal systems have the potential to produce a range of organic compounds through Fischer-Tropsch type (FTT) chemistry. The distribution of products depends on several factors, including the abundance and composition of feedstock molecules, reaction temperature, and the physical and chemical characteristics of catalytic materials included in the reactions. The majority of studies per-formed to date have focused solely on inclusion of CO2 or CO and H2 as the carbon, oxygen and hydrogen sources, which limits the possible products to hydrocarbons, alcohols and carboxylic acids. A few studies have included nitrogen in the form of ammonia, which led to the production of amino acids and nitrogenous bases. Although these demonstrations provide compelling evidence that FTT reactions can produce compounds of interest for the origins of life, such reactions have been conducted under a very limited range of conditions and the synthetic reaction mechanisms have generally not been well-characterized. We have begun a series of laboratory experiments that will incorporate a range of precursor molecules in varying compositions to determine how these variables affect the relative amounts and speciation of life-essential elements in organic molecules produced under FTT conditions. In the present work, we focus on systems containing C, H, O and N. Reaction mixtures contained CO (~60-80 mM), 150 mM ammonium chloride, and water with a native iron catalyst, which also served as a source of H2 through the reduction of water. Three initial experiments were conducted at 110, 154 and 185 °C and heated for several days. Following the reaction, samples were analyzed by gas chromatography-mass spectrometry, direct analysis in real time mass spectrometry and liquid chromatography-mass spectrometry.

A. S. Burton↗
NASA NTRS2020

A Sensitive Quantitative Analysis of Abiotically Synthesized Short Homopeptides using Ultraperformance Liquid Chromatography and Time-of-Flight Mass Spectrometry

In the origins of life field understanding the abiotic polymerization of simple organic monomers (e.g., amino acids) into larger biomolecules (e.g., oligopeptides), remains a seminal challenge. Recently, preliminary observations showed a limited set of peptides formed in the presence of the plausible prebiotic phosphorylating agent, diamidophosphate (DAP), highlighting the need for an analytical tool to critically evaluate the ability of DAP to induce oligomerization of simple organics under aqueous conditions. However, performing accurate and precise, targeted analyses of short oligopeptides remains a distinct challenge in the analytical chemistry field. Here, we developed a new technique to detect and quantitate amino acids and their homopeptides in a single run using ultraperformance liquid chromatography-fluorescence detection/time of flight mass spectrometry. Over an 8-minute retention time window, 18 target analytes were identified and quantitated, 16 of which were chromatographically separated at, or near baseline resolution. Compound identity was confirmed by accurate mass analysis using a 10 ppm mass tolerance window. This method featured limits of detection < 5 nM (< 1 fmol on column) and limits of quantitation (LOQs) <15 nM (< 3 fmol on column). The LODs and LOQs were upwards of ∼28x and ∼788x lower, respectively, than previous methods for the same analytes, highlighting the quantifiable advantages of this new method. Both detectors provided good quantitative linearity (R(exp 2) > 0.985) for all analytes spanning concentration ranges ∼3 - 4 orders of magnitude. We performed a series of laboratory experiments to investigate DAP-mediated oligomerization of amino acids and peptides and analyzed experimental products with the new method. DAP readily polymerized amino acids and peptides under a range of simulated environmental conditions. This research underscores the potential of DAP to have generated oligopeptides on the primordial Earth, enhancing prebiotic chemical diversity and complexity at or near the origin of life.

Prebiotic Chemistry and Analytical Chemistry↗
NASA NTRSDate not supplied

A Brief Review of Equivalent Available Pressure Measurement and Purpose

This presentation is intended as a lead to a workshop on the subject of Equivalent Available Pressure (EAP). EAP is a concept that has been introduced to the Pressure Gain Combustion (PGC) community in recent years. It is a technique for determining an equivalent steady state figure of merit from the fundamentally unsteady PGC process. The workshop is centered on reviewing the efforts by various organizations to implement the EAP technique specifically on rotating detonation engines (RDE's). RDE's are a type of PGC device. This presentation is a very brief (15 minute) review of the EAP technique for both computational simulations and laboratory experiments. The mathematical equations required to compute EAP are shown and an example RDE simulation is presented showing results.

combustion↗
NASA NTRSDate not supplied

Formation, Survival and Evolution of Organics After Impact Processing of Asteroidal and Cometary Simulants

This work examines the formation and evolution of amino acids during impact events on the prebiotic Earth Laboratory experiments, which simulate impact processes, provide direct tests of questions regarding the conditions (concentration of amino acid, shock stress or impact velocity, matrix material) under which amino acid synthesis and polymerization occur.

exobiology↗
NASA NTRS2020

Infrared spectra and optical constants of astronomical ices: III. Propane, propylene, and propyne

Infrared (IR) spectra of the hydrocarbon ices C3H8 (propane), C3H6 (propylene, propene), and C3H4 (propyne, methylacetylene) are relevant to the study of the low-temperature chemistry and spectroscopy of objects within and beyond the Solar System, but IR band strengths and absorption coefficients are lacking for these compounds. Here we present new IR spectra of crystalline and non-crystalline forms of C3H8, C3H6, and C3H4. Measurements of ice density and refractive index also are reported, two quantities needed to compute IR absorption coefficients, band strengths, optical constants, and, ultimately, abundances of propane, propylene, and propyne in extraterrestrial environments and in laboratory experiments. Suggestions and interpretations are offered regarding the multiple crystalline forms of propane and propylene observed. Applications and extensions are described.

Reggie L. Hudson↗
NASA NTRS2021

Transient evolution of basal drag during glacier slip

Glacier slip is usually described using steady-state sliding laws that relate drag, slip velocity and effective pressure, but where subglacial conditions vary rapidly transient effects may influence slip dynamics. Here we use results from a set of laboratory experiments to examine the transient response of glacier slip over a hard bed to velocity perturbations. The drag and cavity evolution from lab experiments are used to parameterize a rate-and-state drag model that is applied to observations of surface velocity and ice-bed separation from the Greenland ice sheet. The drag model successfully predicts observed lags between changes in ice-bed separation and sliding speed. These lags result from the time (or displacement) required for cavities to evolve from one steady-state condition to another. In comparing drag estimates resulting from applying rate-and-state and steady-state slip laws to transient data, we find the peaks in drag are out of phase. This suggests that in locations where subglacial conditions vary on timescales shorter than those needed for cavity adjustment transient slip processes control basal drag.

Glacier↗
NASA NTRS2020

Infrared Spectra and Optical Constants of Astronomical Ices: III. Propane, Propylene, and Propyne

Infrared (IR) spectra of the hydrocarbon ices C3H8 (propane), C3H6 (propylene, propene), and C3H4 (propyne, methylacetylene) are relevant to the study of the low-temperature chemistry and spectroscopy of objects within and beyond the Solar System, but IR band strengths and absorption coefficients are lacking for these compounds. Here we present new IR spectra of crystalline and non-crystalline forms of C3H8, C3H6, and C3H4. Measurements of ice density and refractive index also are reported, two quantities needed to compute IR absorption coefficients, band strengths, optical constants, and, ultimately, abundances of propane, propylene, and propyne in extraterrestrial environments and in laboratory experiments. Suggestions and interpretations are offered regarding the multiple crystalline forms of propane and propylene observed. Applications and extensions are described.

Ices↗
NASA NTRS2021

Stress-Activated Electric Currents in Icy Planetary Bodies: H2O2-Doped H2O Ices

Planetary satellites such as the Jovian moon Europa and several Kuiper Belt objects (including Pluto) have surfaces consisting largely of H2O ice, which is brittle and behaves as a rock at the low temperatures that prevail in the outer Solar System. Several of those ice-crusted bodies show evidence of tectonic activity indicating high levels of stress. This paper reports on laboratory experiments with pure H2O ice and H2O2–doped H2O ices with H2O2 concentration levels comparable to those in the ices of Europa. Elongated rectangular ice blocks at T = −81 °C [192 K] were stressed at one end to test whether electric currents are generated and capable of flowing down the stress gradient. Pure H2O ice was found to not produce currents above the 10−10 A background level except for occasional transients in the 10−9–10−8 A range during fracture or rapid plastic deformation due to electrons, e’. By contrast, stressing H2O2-doped H2O ices consistently produced electric currents in the 10−7–10−5 A range, due to holes, h•, propagating from the stressed end to the unstressed end. The h• charge carriers are generated by the break-up of peroxy bonds of H2O2 molecules, leading to O−, equivalent to defect electrons or holes h• in the O2− matrix.

Water ice↗
NASA NTRS2020

Infrared spectra and optical constants of astronomical ices: III. Propane, propylene, and propyne

Infrared (IR) spectra of the hydrocarbon ices C3H8 (propane), C3H6 (propylene, propene), and C3H4 (propyne, methylacetylene) are relevant to the study of the low-temperature chemistry and spectroscopy of objects within and beyond the Solar System, but IR band strengths and absorption coefficients are lacking for these compounds. Here we present new IR spectra of crystalline and non-crystalline forms of C3H8, C3H6, and C3H4. Measurements of ice density and refractive index also are reported, two quantities needed to compute IR absorption coefficients, band strengths, optical constants, and, ultimately, abundances of propane, propylene, and propyne in extrater-restrial environments and in laboratory experiments. Suggestions and interpretations are offered regarding the multiple crystalline forms of propane and propylene observed. Applications and extensions are described.

Reggie L. Hudson↗
NASA NTRSDate not supplied

The Stop-and-Go Mechanism: Towards an Integrated Approach to Model Seismicity, Outgassing, Deformation, and Thermal Unrest at Active Volcanoes

Connecting the geophysical and geochemical signals recorded at and above the surface of volcanoes with source mechanisms is fundamental to understand transitions from quiescence to eruption, and to integrate the behavior of volcanoes with their regional seismotectonic and hydrological context. Some of these signals include shallow volcanic tremor, a long-lasting (minutes-to-years) ground vibration detected in volcanic areas during unrest; volcanic outgassing, which shows intriguing periodicities over multiple scales, as revealed by space-borne instruments and by ground-based, high-frequency (~1 Hz), sampling methods; inflation and deflation of volcanic edifices, commonly associated with subsurface volume changes; and large-scale (from a few to tens of km2), low-temperature, thermal anomalies, a newly-discovered signal that has been observed to emerge on volcanic flanks from months-to-years prior to gas- and magma-driven eruptions. Traditionally, these geophysical and geochemical signals have been modelled independently, which limits our interpretation of subsurface processes and thus our assessment of unrest. In this work, we show through lumped-parameter models, numerical simulations, and preliminary laboratory experiments that many of the signals recorded around volcanoes can be integrated into a common “stop-and-go” mechanism. In particular, we found that they can arise spontaneously when taking into account the feedbacks between the temporary accumulation of gas and/or magma in the crust (“stop”), and the diffusive transfer of gas and heat towards the surface (“go”). For example, we find that the “stop-and-go” mechanism can explain: (i) the emergence of monochromatic, broadband, and harmonic tremor; (ii) the periodic components commonly observed in volcanic outgassing time series; (iii) the link between large-scale thermal anomalies and shallow hydrothermal systems; (iv) the reported time lags between large-scale thermal anomalies and deformation; and (v) the breathing of potentially destructive volcanic calderas. The “stop-and-go” mechanism provides a consistent and realistic framework to link multiple geophysical and geochemical signals with the processes leading to volcanic unrest and eruption.

volcanoes↗
NASA NTRS2020

Infrared Spectra and Optical Constants of Astronomical Ices: III. Propane, Propylene, and Propyne

Infrared (IR) spectra of the hydrocarbon ices C3H8 (propane), C3H6 (propylene, propene), and C3H4 (propyne, methylacetylene) are relevant to the study of the low-temperature chemistry and spectroscopy of objects within and beyond the Solar System, but IR band strengths and absorption coefficients are lacking for these compounds. Here we present new IR spectra of crystalline and non-crystalline forms of C3H8, C3H6, and C3H4. Measurements of ice density and refractive index also are reported, two quantities needed to compute IR absorption coefficients, band strengths, optical constants, and, ultimately, abundances of propane, propylene, and propyne in extraterrestrial environments and in laboratory experiments. Suggestions and interpretations are offered regarding the multiple crystalline forms of propane and propylene observed. Applications and extensions are described.

Reggie L Hudson↗
NASA NTRS2022

Identifying the Wide Diversity of Extraterrestrial Purine and Pyrimidine Nucleobases in Carbonaceous Meteorites

The lack of pyrimidine diversity in meteorites remains a mystery since prebiotic chemical models and laboratory experiments have predicted that these compounds can also be produced from chemical precursors found in meteorites. Here we report the detection of nucleobases in three carbonaceous meteorites using state-of-the-art analytical techniques optimized for small-scale quantification of nucleobases down to the range of parts per trillion (ppt). In addition to previously detected purine nucleobases in meteorites such as guanine and adenine, we identify various pyrimidine nucleobases such as cytosine, uracil, and thymine, and their structural isomers such as isocytosine, imidazole-4-carboxylic acid, and 6-methyluracil, respectively. Given the similarity in the molecular distribution of pyrimidines in meteorites and those in photon-processed interstellar ice analogues, some of these derivatives could have been generated by photochemical reactions prevailing in the interstellar medium and later incorporated into asteroids during solar system formation. This study demonstrates that a diversity of meteoritic nucleobases could serve as building blocks of DNA and RNA on the early Earth.

Yasuhiro Oba↗
NASA NTRSDate not supplied

Suborbital Testing of the OSCAR Trash-to-Gas System

With the sustained human exploration of nearby celestial bodies on the horizon, a renewed outlook on crew waste management must be realized. Current waste management strategies aboard the International Space Station become impractical as we venture beyond low Earth orbit. Furthermore, for future exploration missions, extracting resources from various waste streams becomes increasingly advantageous. One method of combatting the long-duration waste management problem is by thermally degrading solid and liquid crew waste items into a chemically inert, ventable gas stream, a process known as Trash-to-Gas. The Orbital Syngas/Commodity Augmentation Reactor (OSCAR) is the state-of-the-art Trash-to-Gas system which has been designed to explore microgravity Trash-to-Gas concepts for improved mass/volume reduction and resource recovery from waste. OSCAR is a subscale testbed design that supports the NASA Logistics Reduction project under the Advanced Exploration Systems Program and Space Technology Mission Directorate Flight Opportunities Program to determine the feasibility of Trash-to-Gas technology for future use on long duration space missions. OSCAR has flown on two suborbital flight demonstrations aboard Blue Origin’s New Shepard launch vehicle. This paper presents a high-level comparative analysis of these microgravity test campaigns with Earth gravity laboratory experiments. Solid-to-gas conversion, gas production & composition, and reactor temperature & pressure are compared to highlight the operational factors and performance differences within the microgravity environment for future optimization.

Ray P Pitts↗
NASA NTRSDate not supplied

Onboard Doppler Compensation for Low-Rate Communications over Commercial Relay Satellites

NASA spacecraft performing scientific and exploration missions may increasingly communicate over commercial relay satellites, including those that operate at Ka-band. Ideally these spacecraft could use the same Ka-band terminal for low-rate telemetry/commanding. However, this use case presents an issue since most commercial relay systems were designed with terrestrial users in mind and cannot easily handle the Doppler effects of orbiting spacecraft. In this work we propose onboard Doppler compensation allowing spacecraft to use existing relay satellite infrastructure without modification. Specifically, we present a method for digital compensation based on a series of piecewise linear sweeps which minimizes resources used on the spacecraft’s radio. We perform orbital mechanics simulations to estimate the worst-case Doppler profiles experienced by spacecraft in several low-Earth orbits. We emulate these effects in a laboratory experiment and demonstrate the proposed technique will reduce Doppler effects by more than two orders of magnitude. The residual Doppler is small enough that modems used at commercial relay sites are able to receive error-free data even when operating at their lowest supported symbol rate.

Adam Gannon↗