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NASA NTRS2016

Impact of Scattering Model on Disdrometer Derived Attenuation Scaling

NASA Glenn Research Center (GRC), the Air Force Research Laboratory (AFRL), and the Politecnico di Milano (POLIMI) are currently entering the third year of a joint propagation study in Milan, Italy utilizing the 20 and 40 GHz beacons of the Alphasat TDP#5 Aldo Paraboni scientific payload. The Ka- and Q-band beacon receivers were installed at the POLIMI campus in June of 2014 and provide direct measurements of signal attenuation at each frequency. Collocated weather instrumentation provides concurrent measurement of atmospheric conditions at the receiver; included among these weather instruments is a Thies Clima Laser Precipitation Monitor (optical disdrometer) which records droplet size distributions (DSD) and droplet velocity distributions (DVD) during precipitation events. This information can be used to derive the specific attenuation at frequencies of interest and thereby scale measured attenuation data from one frequency to another. Given the ability to both predict the 40 gigahertz attenuation from the disdrometer and the 20 gigahertz time-series as well as to directly measure the 40 gigahertz attenuation with the beacon receiver, the Milan terminal is uniquely able to assess these scaling techniques and refine the methods used to infer attenuation from disdrometer data. In order to derive specific attenuation from the DSD, the forward scattering coefficient must be computed. In previous work, this has been done using the Mie scattering model, however, this assumes a spherical droplet shape. The primary goal of this analysis is to assess the impact of the scattering model and droplet shape on disdrometer-derived attenuation predictions by comparing the use of the Mie scattering model to the use of the T-matrix method, which does not assume a spherical droplet. In particular, this paper will investigate the impact of these two scattering approaches on the error of the resulting predictions as well as on the relationship between prediction error and rain rate.

Radio Transmission↗

NASA NTRS2017

Application of New Partition Coefficients to Modeling Plagioclase

Previously, studies that determined the partition coefficient for an element, i, between plagioclase and the residual basaltic melt (Di plag) have been conducted using experimental conditions dissimilar from the Moon, and thus these values are not ideal for modeling plagioclase fractionation in a lunar system. However, recent work [1] has determined partition coefficients for plagioclase at lunar oxygen fugacities, and resulted in plagioclase with Anorthite contents ≥An90; these are significantly more calcic than plagioclase in previous studies, and the An content has a profound effect on partition coefficient values [2,3]. Plagioclase D-values, which are dependent on the An content of the crystal [e.g., 2-6], can be determined using published experimental data and the correlative An contents. Here, we examine new experimental data from [1] to ascertain their effect on the calculation of equilibrium liquids from Apollo 16 sample 60635,2. This sample is a coarse grained, subophitic impact melt composed of ~55% plagioclase laths with An94.4-98.7 [7,8], distinctly more calcic than of previous partition coefficient studies (e.g., [3-6, 9-10]). Sample 60635,2 is notable as having several plagioclase trace element analyses containing a negative Europium anomaly (-Eu) in the rare-earth element (REE) profile, rather than the typical positive Eu anomaly (+Eu) [7-8] (Fig. 1). The expected +Eu is due to the similarity in size and charge with Ca2+, thereby allowing Eu2+ to be easily taken up by the plagioclase crystal structure, in contrast to the remaining REE3+. Some 60635,2 plagioclase crystals only have +Eu REE profiles, some only have -Eu REE profiles, and some +Eu and -Eu analyses in different areas on a single crystal [7, 8]. Moreover, there does not seem to be any core-rim association with the +Eu or -Eu analyses, nor does there appear to be a correlation between the size, shape, or location of a particular crystal within the sample and the sign of its Eu anomaly, which suggests a complex evolution. In order to investigate this sample further, we can calculate the equilibrium liquids, but with An contents distinct from previous experimental studies, we must calculate the appropriate partition coefficients for each trace element analysis.

Fagan, A. L.↗

NASA NTRS2017

Influence of Oxychlorine Phases During the Pyrolysis of Organic Molecules: Implications for the Quest of Organics on Mars with the SAM Experiment Onboard the Curiosity Rover

One among the main objectives of the Sample Analysis at Mars (SAM) experiment is the in situ molecular analysis of gases evolving from solid samples heated up to approximately 850 degrees Centigrade, and collected by Curiosity on Mars surface/sub-surface in Gale crater. With this aim, SAM uses a gas-chromatograph coupled to a quadrupole mass spectrometer (GC-QMS) devoted to separate, detect and identify both volatile inorganic and organic compounds. SAM detected chlorinated organic molecules produced in evolved gas analysis (EGA) experiments. Several of these were also detected by the Viking experiments in 1976. SAM also detected oxychlorine compounds that were present at the Phoenix landing site. The oxychlorines may be prevelant over much of the martian surface. The C1 to C3 aliphatic chlorohydrocarbons (chloromethane and di- and trichloromethane) detected by SAM were attributed to reaction products occurring between the oxychlorines phases and the organic compounds coming from SAM instrument background. But SAM also showed the presence of a large excess of chlorobenzene and C2 to C4 dichloroalkanes among the volatile species released by the Cumberland sample of the Sheepbed mudstone. For the first time in the history of the Mars exploration, this proved the presence of Mars indigenous organic material at the Mars' surface. However, the identification of the precursor organic compounds of these chlorohydrocarbons is difficult due to the complexity of the reactions occurring during the sample pyrolysis. Laboratory pyrolysis experiments have demonstrated that oxychlorines phases such as perchlorates and chlorates, decomposed into dioxygen and volatile chlorine bearing molecules (HCl and/or Cl2) during the pyrolysis. These chemical species can then react with the organic molecules present in the martian solid samples through oxidation, chlorination and oxychlorination processes.

Millan, M.↗

NASA NTRS2017

Coastal California's Fog as a Unique Habitable Niche: Design for Autonomous Sampling and Preliminary Aerobiological Characterization

Just as on the land or in the ocean, atmospheric regions may be more or less hospitable to life. The aerobiosphere, or collection of living things in Earth's atmosphere, is poorly understood due to the small number and ad hoc nature of samples studied. However, we know viable airborne microbes play important roles, such as providing cloud condensation nuclei. Knowing the distribution of such microorganisms and how their activity can alter water, carbon, and other geochemical cycles is key to developing criteria for planetary habitability, particularly for potential habitats with wet atmospheres but little stable surface water. Coastal California has regular, dense fog known to play a major transport role in the local ecosystem. In addition to the significant local (1 km) geographical variation in typical fog, previous studies have found that changes in height above surface of as little as a few meters can yield significant differences in typical concentrations, populations and residence times. No single current sampling platform (ground-based impactors, towers, balloons, aircraft) is capable of accessing all of these regions of interest.A novel passive fog and cloud water sampler, consisting of a lightweight passive impactor suspended from autonomous aerial vehicles (UAVs), is being developed to allow 4D point sampling within a single fog bank, allowing closer study of small-scale (100 m) system dynamics. Fog and cloud droplet water samples from low-altitude aircraft flights in nearby coastal waters were collected and assayed to estimate the required sample volumes, flight times, and sensitivity thresholds of the system under design.125 cloud water samples were collected from 16 flights of the Center for Interdisciplinary Remotely Piloted Aircraft Studies (CIRPAS) instrumented Twin Otter, equipped with a sampling tube collector, occurring between 18 July and 12 August 2016 below 1 km altitude off the central coast. The collector was flushed first with 70 ethanol, then with sterile DI water, between sampling regions. Collected volumes ranged from 100 L to 12 mL. All samples were diluted serially and plated on two different types of agar, nutrient-dense (PCA) and sparse (R-2A). Plates were incubated at room temperature and counted when colonies first appeared and again at 2 weeks.Preliminary results from seven flights are consistent with generally reported colony-forming unit (CFU) values for terrestrial fog water (e.g., [4]). The PCA assay ranged from 400 to 125,000 CFU/mL, R-2A from 700 to 130,000 CFU/mL. PCA and R-2A counts were not significantly different from each other at I^ plus or minus +/- 0.05, although observationally, the R2A plates had more pigmented colonies. CFU counts from the majority of flights were not different from each other in mean at the same level of significance, but about half differed in median, indicating differences in underlying distribution. These results validate the presence of viable microorganisms in coastal California fog at levels that should be easily detectable by our sampling system. The indicated distribution differences underscore the need for small-scale, long-term sampling surveys. Future planned work includes ion chromatography for limiting nutrients, ATP quantification, and qPCR for several microbial classes of interest.

Coastal↗

NASA NTRS2016

Impact of Scattering Model on Disdrometer Derived Attenuation Scaling

NASA Glenn Research Center (GRC), the Air Force Research Laboratory (AFRL), and the Politecnico di Milano (POLIMI) are currently entering the third year of a joint propagation study in Milan, Italy utilizing the 20 and 40 GHz beacons of the Alphasat TDP5 Aldo Paraboni scientific payload. The Ka- and Q-band beacon receivers were installed at the POLIMI campus in June of 2014 and provide direct measurements of signal attenuation at each frequency. Collocated weather instrumentation provides concurrent measurement of atmospheric conditions at the receiver; included among these weather instruments is a Thies Clima Laser Precipitation Monitor (optical disdrometer) which records droplet size distributions (DSD) and droplet velocity distributions (DVD) during precipitation events. This information can be used to derive the specific attenuation at frequencies of interest and thereby scale measured attenuation data from one frequency to another. Given the ability to both predict the 40 GHz attenuation from the disdrometer and the 20 GHz timeseries as well as to directly measure the 40 GHz attenuation with the beacon receiver, the Milan terminal is uniquely able to assess these scaling techniques and refine the methods used to infer attenuation from disdrometer data.In order to derive specific attenuation from the DSD, the forward scattering coefficient must be computed. In previous work, this has been done using the Mie scattering model, however, this assumes a spherical droplet shape. The primary goal of this analysis is to assess the impact of the scattering model and droplet shape on disdrometer derived attenuation predictions by comparing the use of the Mie scattering model to the use of the T-matrix method, which does not assume a spherical droplet. In particular, this paper will investigate the impact of these two scattering approaches on the error of the resulting predictions as well as on the relationship between prediction error and rain rate.

statistics↗

NASA NTRS2017

Kinetic Monte Carlo Simulations of Diffusion in Environmental Barrier Coating Materials

Ceramic Matrix Components (CMC) components for use in turbine engines offer a number of advantages compared with current practice. However, such components are subject to degradation through a variety of mechanisms. In particular, in the hot environment inside a turbine in operation a considerable amount of water vapor is present, and this can lead to corrosion and recession. Environmental Barrier Coating (EBC) systems that limit the amount of oxygen and water reaching the component are required to reduce this degradation and extend component life. A number of silicate-based materials are under consideration for use in such coating systems, including Yttterbium and Yttrium di- and monosilicates. In this work, we present results of kinetic Monte Carlo computer simulations of oxygen diffusion in Yttrium disilicate, and compare with previous work on Yttterbium disilicate. Coatings may also exhibit cracking, and the cracks can provide a direct path for oxygen to reach the component. There is typically a bond coat between the coating and component surface, but the bond coat material is generally chosen for properties other than low oxygen diffusivity. Nevertheless, the degree to which the bond coat can inhibit oxygen diffusion is of interest, as it may form the final defense against oxygen impingement on the component. We have therefore performed similar simulations of oxygen diffusion through HfSiO4, a proposed bond coat material.

Computer Simulation↗

NASA NTRS2017

The Amorphous Composition of Three Mudstone Samples from Gale Crater: Implications for Weathering and Diagenetic Processes on Mars

The Mars Science Laboratory rover, Curiosity, is exploring the lowermost formation of Gale crater's central mound. Within this formation, three samples named Marimba, Quela, and Sebina have been analyzed by the CheMin X-ray diffractometer and the Alpha Particle X-ray Spectrometer (APXS) to determine mineralogy and bulk elemental chemistry, respectively. Marimba and Quela were also analyzed by the SAM (Sample Analysis at Mars) instrument to characterize the type and abundance of volatile phases detected in evolved gas analyses (EGA). CheMin data show similar proportions of plagioclase, hematite, and Ca-sulfates along with a mixture of di- and trioctahedral smectites at abundances of approximately 28, approximately 16, and approximately 18 wt% for Marimba, Quela, and Sebina. Approximately 50 wt% of each mudstone is comprised of X-ray amorphous and trace crystalline phases present below the CheMin detection limit (approximately 1 wt%). APXS measurements reveal a distinct bulk elemental chemistry that cannot be attributed to the clay mineral variation alone indicating a variable amorphous phase assemblage exists among the three mudstones. To explore the amorphous component, the calculated amorphous composition and SAM EGA results are used to identify amorphous phases unique to each mudstone. For example, the amorphous fraction of Marimba has twice the FeO wt% compared to Quela and Sebina yet, SAM EGA data show no evidence for Fe-sulfates. These data imply that Fe must reside in alternate Fe-bearing amorphous phases (e.g., nanophase iron oxides, ferrihydrite, etc.). Constraining the composition, abundances, and proposed identity of the amorphous fraction provides an opportunity to speculate on the past physical, chemical, and/or diagenetic processes which produced such phases in addition to sediment sources, lake chemistry, and the broader geologic history of Gale crater.

Achilles, C. N.↗

NASA NTRS2014

Identification of Flights for Cost-Efficient Climate Impact Reduction

The aircraft-induced climate impact has drawn attention in recent years. Aviation operations affect the environment mainly through the release of carbon-dioxide, nitrogen-oxides, and by the formation of contrails. Recent research has shown that altering trajectories can reduce aviation environmental cost by reducing Absolute Global Temperature Change Potential, a climate assessment metric that adapts a linear system for modeling the global temperature response to aviation emissions and contrails. However, these methods will increase fuel consumption that leads to higher fuel costs imposed on airlines. The goal of this work is to identify ights for which the environmental cost of climate impact reduction outweighs the increase in operational cost on an individual aircraft basis. Environmental cost is quanti ed using the monetary social cost of carbon. The increase in operational cost is considering cost of additional fuel usage only. For this paper, an algorithm has been developed that modi es the trajectories of ights to evaluate the e ect of environ- mental cost and operational cost of ights in the United States National Airspace System. The algorithm identi es ights for which the environmental cost of climate impact can be reduced and modi es their trajectories to achieve maximum environmental net bene t, which is the di erence between reduction in environmental cost and additional operational cost. The result shows on a selected day, 16% of the ights among eight major airlines, or 2,043 ights, can achieve environmental net bene t using weather forecast data, resulting in net bene t of around $500,000. The result also suggests that the long-haul ights would be better candidates for cost-ecient climate impact reduction than the short haul ights. The algorithm will help to identify the characteristics of ights that are capable of applying cost-ecient climate impact reduction strategy.

climate impact reduction↗

NASA NTRS2018

Development and Documentation of kL-Based Linear, Nonlinear, and Full Reynolds Stress Turbulence Models

The development and implementation of kL-based Reynolds Average Navier-Stokes (RANS) turbulence models are reported herein. The kL is based on Abdol-Hamid's closure and Menter's modi cation to Rotta's two-equation model. Rotta shows that a reliable transport equation can be formed from the turbulent length scale L, and the turbulent kinetic energy k. Rotta's kL equation is well suited for term-by-term modeling and displays useful features compared to other scale formulation. One of the important di erences is the inclusion of higher order velocity derivatives in the source terms of the scale equation. This can enhance the ability of RANS solvers to simulate unsteady ows in URANS mode. The present report documents the formulation of three model levels of turbulence models as implemented in the CFD code FUN3D. Methodology and calibration examples are shown in detail. The levels are the linear k-kL and the two-equation algebraic Reynolds stress model (ARSM) as well as the full Reynolds Stress Model (RSM). Attached, separated and corner ow cases are documented and compared with experimental, theoretical and other turbulence model data. The results show generally very good comparisons with canonical and experimental data. The results from this formulation are similar or better than results using the SST two- equation turbulence model. ARSM shows great promise with similar level of computational resources as general two equation turbulence models.

Abdol-Hamid, Khaled S.↗

NASA NTRS2018

Three Years of Atmospheric Characterization at Ka/Q-band with the NASA/POLIMI Alphasat Receiver in Milan, Italy

Since June of 2014, NASA Glenn Research Center (GRC) and the Politecnico di Milano (POLIMI) have jointly conducted a propagation campaign within the framework of the Alphasat propagation experiment through a propagation terminal at the POLIMI campus in Milan, Italy. The terminal utilizes the 20 GHz and 40 GHz beacons broadcast by the Aldo Paraboni Technology Demonstration Payload (TDP #5), and consists of dual coherent Ka- and Q-band beacon receivers. These provide a direct measurement of the signal attenuation and scintillation and are complemented by concurrent weather instrumentation that provides measurements of the atmospheric conditions at the receiver. The primary goal of these measurements is to improve model predictions of communication system performance at 40 GHz. Over three years of concurrent measurements have now been collected from the terminal, and herein we present a statistical analysis of the results thus far, as well as a summary of recent hardware upgrades to the receivers that were made in September 2017.

Radio Transmission↗

NASA NTRS2013

A New Nearby Pulsar Wind Nebula Overlapping the RX J0852.0-4622 Supernova Remnant

Context. Energetic pulsars can be embedded in a nebula of relativistic leptons which is powered by the dissipation of the rotational energy of the pulsar. The object PSR J0855􀀀4644 is an energetic and fast-spinning pulsar (E' = 1.1 x 10(exp 36) erg/s, P=65 ms) discovered near the South-East rim of the supernova remnant (SNR) RXJ0852.0-4622 (aka Vela Jr) by the Parkes multibeam survey. The position of the pulsar is in spatial coincidence with an enhancement in X-rays and TeV gamma-rays, which could be due to its putative pulsar wind nebula (PWN). Aims. The purpose of this study is to search for di use non-thermal X-ray emission around PSR J0855-4644 to test for the presence of a PWN and to estimate the distance to the pulsar. Methods. An X-ray observation was carried out with the XMM-Newton satellite to constrain the properties of the pulsar and its nebula. The absorption column density derived in X-rays from the pulsar and from different regions of the rim of the SNR was compared with the absorption derived from the atomic (HI) and molecular ((12)CO) gas distribution along the corresponding lines of sight to estimate the distance to the pulsar and to the SNR. Results. The observation has revealed the X-ray counterpart of the pulsar together with surrounding extended emission thus confirming the existence of a PWN. The comparison of column densities provided an upper limit to the distance of the pulsar PSR J0855-4644 and the SNR RX J0852.0-4622 (d less than or equal to 900 pc). Although both objects are at compatible distances, we rule out that the pulsar and the SNR are associated. With this revised distance, PSR J0855-4644 is the second most energetic pulsar, after the Vela pulsar, within a radius of 1 kpc and could therefore contribute to the local cosmic-ray e-/e+ spectrum.

overlapping↗

NASA NTRS2017

A View from Above: Earth Observations

Since the 1960s, satellites have been looking down at the Earth to monitor weather patterns and track severe storms, observe how our land surface is changing and responding to hydrometerological extremes, and even to sense how the Earth's crust is deforming from earthquakes and volcanoes. Space and airborne platforms can provide unique views of the disaster lifecycle, informing pre-event mitigation and preparedness, emergency response following an event, and monitoring longer-term recovery. These remotely-sensed data, products and models can provide a global perspective to see beyond administrative boundaries, reach remote places where in situ observations are di cult or non-existent, and provide the necessary context and situational awareness to aid in disaster response. So how do these platforms work? Instruments aboard satellites use different portions of the electromagnetic spectrum to passively or actively observe energy across a range of wavelengths, which can be turned into meaningful data on geophysical, atmospheric, and hydrological variables. e US has had a broad range of Earth observation (EO) platforms delivering open data for scientific research and societal benefits for decades. e Landsat programme, a joint initiative between the US Geological Survey (USGS) and NASA, has the world's longest continuous collection of space-based satellite imagery of the Earth, extending from 1972 to present. e Landsat satellites provide visible, near infrared, and thermal data that are used to support emergency response and disaster relief by mapping changes in water during floods, and dramatic land surface changes, including those resulting from landslides, wild res, severe weather, volcanic plumes, and dust storms.

FEMA↗

NASA NTRS2018

E-Beam Generated Plasma Etching for Developing High-Reflectance Mirrors for Far-Ultraviolet Astronomical Instrument Applications

Astronomical space telescopes to study astrophysical phenomena from the far-ultraviolet (FUV) to the near infrared (NIR) will require mirror coatings with high reflectance over this entire spectral region. While coatings for the optical and NIR part of the spectrum are fairly well developed with proven performance, the FUV presents significant challenges. The U.S. Naval Research Laboratory (NRL) has developed a processing system based on an electron beam-generated plasma that provides for controlled fluorination and/or etching of surfaces with near monolayer precision and minimal changes to surface morphology. In this paper, we report recent results of samples treated in the NRL Large Area Plasma Processing System (LAPPS) where restoration of the high intrinsic reflectance in the FUV spectral range have been observed of aluminum (Al) mirrors protected with a magnesium di-fluoride (MgF2) overcoat. This paper will also extend these studies to other Al mirrors protected with aluminum tri-fluoride (AlF3) in order to realize the high intrinsic reflectance Al down to FUV wavelengths (100−200 nm), while still maintaining the high reflectance in the optical and NIR spectral regions. Laboratory test data and optical diagnostic techniques used to verify surface scattering and durability of selected coatings will be presented. Finally, we will discuss the scalability of the LAPPS etching process in order to realize these high-reflectivity coatings on mirror segments as large as those proposed for the Large Ultraviolet, Optical, and Infrared (LUVOIR) astronomical telescope system (1+meter class).

LUVOIR↗

NASA NTRS2018

Three Years of Atmospheric Characterization at Ka/Q-band with the NASA/POLIMI Alphasat Receiver in Milan, Italy

Radio Transmission↗

NASA NTRS2018

N2 Chemistry in Interstellar and Planetary Ices: Radiation-Driven Oxidation

As part of our work on nitrogen-rich ices, the IR spectra and band strengths used in a recent paper to identify and quantify radiation-induced changes in an N2+H2O ice near 15 K are examined, along with reports of (i) a chemical tracer for N2+H2O ices, (ii) a new IR feature of solid N2, and (iii) a striking 15N isotopic enrichment. Problems are found for each IR band strength used and for each of the three claims made, to the extent that none are supported by the results presented to date. In contrast, new work presented here, combined with several older investigations, strongly supports the formation of di- and triatomic nitrogen oxides in irradiated N2-rich ices. Observations and trends in the chemistry of N2-rich icy solids are described, and conclusions are drawn. A considerable amount of material from previous chemical studies of N2-rich systems, spanning more than a century, is brought together for the rst time and used to examine the chemistry of N2-rich ices in extraterrestrial environments. Needs are identied and suggestions made for future studies of N2-rich interstellar and planetary ice analogs.

astrobiology↗

NASA NTRS2019

Full Inversion of Solar Relativistic Electron Events Measured by the Helios Spacecraft

The Parker Solar Probe and the incoming Solar Orbiter mission will provide measurements of solar energetic particle (SEP) events at close heliocentric distances from the Sun. Up to present, the largest data set of SEP events in the inner heliosphere are the observations by the two Helios spacecraft. Aims.We re-visit a sample of 15 solar relativistic electron events measured by the Helios mission with the goal of better characterizing the injection histories of solar energetic particles and their interplanetary transport conditions at heliocentric distances <1AU. Methods. The measurements provided by the E6 instrument on board Helios provide us with the electron directional distributionsin eight di erent sectors that we use to infer the detailed evolution of the electron pitch-angle distributions. The results of a Monte Carlo interplanetary transport model, combined with a full inversion procedure, were used to fit the observed directional intensities in the 300â€“800 keV nominal energy channel. Unlike previous studies, we have considered both the energy and angular responses of the detector. This method allowed us to infer the electron release time profile at the source and determine the electron interplanetary transport conditions. Results. We discuss the duration of the release time profiles and the values of the radial mean free path, and compare them with thevalues reported previously in the literature using earlier approaches. Five of the events show short injection histories (<30 min) at the Sun and ten events show long-lasting (>30 min) injections. The values of mean free path range from 0.02AU to 0.27AU.Conclusions. The inferred injection histories match with the radio and soft X-ray emissions found in literature.We find no dependence of the radial mean free path on the radial distance. In addition, we find no apparent relation between the strength of interplanetary scattering and the size of the solar particle release.

Pacheco, D.↗

NASA NTRS2019

Finding Evidence of a Prebiotic Pyruvate Reaction Network in Meteorites

The organic compounds of carbonaceous chondrites are structurally diverse products of the prolonged abiotic chemistry that occurred before and during the early stages of the solar system. They also represent the types of prebiotic compounds that may have participated in chemical evolutionary processes that gave rise to life. Pyruvic acid is a key component of primary metabolism that has recently been found in carbonaceous chondrites. Its prominence in biology has inspired us to explore its chemistry and possible role in the origin of metabolism. Our laboratory investigations have found that pyruvate (the ionized form of pyruvic acid) can serve as a single-source reactant to generate what we term a pyruvate reaction network (PRN). The core of the PRN is driven by pyruvate aldol polymerization and decay reactions. These decay reactions lead to the production of stable and unstable compounds which include mono, di, and tricarboxylic acids and a variety of keto acids. Importantly, many of these reactions apparently lead back to pyruvate, establishing a feedback process. Finding evidence of this reaction network in meteorites would establish that the chemistry of pyruvate did occur in a prebiotic environment and indeed many of the known compounds found in pyruvate reaction mixtures were detected in the Murchison and Murray meteorites. However, multiple synthetic origins, not tied to pyruvate chemistry, might also explain their meteoritic presence. Thus finding compounds unique to the PRN, such as reaction intermediates, would provide stronger evidence in support of its prebiotic relevance. The identity of these intermediates can only be con-firmed by acquiring chemical standards, however, as most are not available commercially, we engaged in extensive chemical synthesis. Obtaining these standards also provides the opportunity to study their subsequent chemistry and roles in the PRN.

Rios, A. C.↗

NASA NTRS2019

Finding Evidence of a Prebiotic Pyruvate Reaction Network in Meteorites

The organic compounds of carbonaceous chondrites are structurally diverse products of the prolonged abiotic chemistry that occurred before and during the early stages of the solar system. They also represent the types of prebiotic compounds that may have participated in chemical evolutionary processes that gave rise to life. Pyruvic acid is a key component of primary metabolism that has recently been found in carbonaceous chondrites. Its prominence in biology has inspired us to explore its chemistry and possible role in the origin of metabolism. Our laboratory investigations have found that pyruvate (the ionized form of pyruvic acid) can serve as a single-source reactant to generate what we term a pyruvate reaction network (PRN). The core of the PRN is driven by pyruvate aldol polymerization and decay reactions. These decay reactions lead to the production of stable and unstable compounds which include mono, di, and tricarboxylic acids and a variety of keto acids. Importantly, many of these reactions apparently lead back to pyruvate, establishing a feedback process. Finding evidence of this reaction network in meteorites would establish that the chemistry of pyruvate did occur in a prebiotic environment and indeed many of the known compounds found in pyruvate reaction mixtures were detected in the Murchison and Murray meteorites. However, multiple synthetic origins, not tied to pyruvate chemistry, might also explain their meteoritic presence. Thus finding compounds unique to the PRN, such as reaction intermediates, would provide stronger evidence in support of its prebiotic relevance. The identity of these intermediates can only be confirmed by acquiring chemical standards, however, as most are not available commercially, we engaged in extensive chemical synthesis. Obtaining these standards also provides the opportunity to study their subsequent chemistry and roles in the PRN.

Rios, Andro↗