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NASA NTRS2013

A Search for Amino Acids and Nucleobases in the Martian Meteorite Roberts Massif 04262 Using Liquid Chromatography-Mass Spectrometry

The investigation into whether Mars contains signatures of past or present life is of great interest to science and society. Amino acids and nucleobases are compounds that are essential for all known life on Earth and are excellent target molecules in the search for potential Martian biomarkers or prebiotic chemistry. Martian meteorites represent the only samples from Mars that can be studied directly in the laboratory on Earth. Here, we analyzed the amino acid and nucleobase content of the shergottite Roberts Massif (RBT) 04262 using liquid chromatography-mass spectrometry. We did not detect any nucleobases above our detection limit in formic acid extracts; however, we did measure a suite of protein and nonprotein amino acids in hot-water extracts with high relative abundances of beta-alanine and gamma-amino-eta-butyric acid. The presence of only low (to absent) levels of several proteinogenic amino acids and a lack of nucleobases suggest that this meteorite fragment is fairly uncontaminated with respect to these common biological compounds. The distribution of straight-chained amine-terminal eta-omega-amino acids in RBT 04262 resembled those previously measured in thermally altered carbonaceous meteorites. A carbon isotope ratio of -24(0/00) +/- 6(0/00) for beta-alanine in RBT 04262 is in the range of reduced organic carbon previously measured in Martian meteorites (Steele et al. 2012). The presence of eta-omega-amino acids may be due to a high temperature Fischer-Tropschtype synthesis during igneous processing on Mars or impact ejection of the meteorites from Mars, but more experimental data are needed to support these hypotheses.

Laboratory analysis↗

NASA NTRS2018

Dragonfly: Investigating the Surface Composition of Titan

Dragonfly is a rotorcraft lander mission, selected as a finalist in NASA's New Frontiers Program, that is designed to sample materials and determine the surface composition in different geologic settings on Titan. This revolutionary mission concept would explore diverse locations to characterize the habitability of Titan's environment, to investigate how far prebiotic chemistry has progressed, and to search for chemical signatures that could be indicative of water-based and/or hydrocarbon-based life. Here we describe Dragonfly's capabilities to determine the composition of a variety of surface units on Titan, from elemental components to complex organic molecules. The compositional investigation ncludes characterization of local surface environments and finely sampled materials. The Dragonfly flexible sampling approach can robustly accommodate materials from Titan's most intriguing surface environments.

Trainer, M. G.↗

NASA NTRS2018

Aerothermodynamics for Dragonfly's Titan Entry

Dragonfly is a proposed spacecraft and mission that would send a mobile robotic rotorcraft lander to Titan, the largest moon of Saturn, in order to study prebiotic chemistry and extraterrestrial habitability at various locations. Titan is unique in having an abundant, complex, and diverse carbon-rich chemistry on the surface of a water-ice-dominated world with an interior water ocean, making it a high priority target for astrobiology and origin of life studies. The mission was initially proposed in April 2017 to NASA's New Frontiers program by the Johns Hopkins Applied Physics Laboratory. In December 2017, it was selected as one of two finalists (out of twelve proposals) to further refine the mission's concept. NASA Ames Research Center and NASA Langley Research Center are partnering as the leads for the Dragonfly's entry system to provide the completed EDL Assembly. The aerothermal analysis for Dragonfly utilizes four simulation tools from NASA Ames Research Center. Traj for calculating the trajectory, DPLR 4.04.0 for calculating the flowfield around the vehicle and convective heating, NEQAIR V15.0 for calculating the radiative heating, and FIAT for calculating the material response and thermal protection system (TPS) sizing for the heatshield. The entry conditions are relatively benign and can readily be accommodated with a tiled PICA heatshield similar to MSL and a number of flight proven materials for the backshell. This work will demonstrate that the aerothermal entry environments can be readily solved using heritage materials and techniques.

New Frontiers↗

NASA NTRS2020

Apollo Next Generation Sample Analysis (ANGSA): A Segue to the Next Era of Lunar Exploration and Sample Return Activities

In the fifty years since the first lunar samples were collected on Apollo 11, significant advancements have taken place in laboratory analysis, planetary science, and astromaterials curation. These advances are now being leveraged for the Apollo Next Generation Sample Analysis (ANGSA) Program, which aims to study specially curated Apollo samples that have never been studied before. Since Apollo 17 in 1972, a great deal has been learned about the Moon, including the unique environments of the poles. Building upon Apollo and remote sensing studies since then, the Artemis Program aims to explore the cold environments near the lunar south pole while achieving the concurrent goals of landing the first woman and the next man on the Moon by 2024. Recent developments for ANGSA have significantly accelerated our readiness for Artemis sample return, particularly in the area of cold sample studies. Four science teams were selected to study cold and/or volatile-bearing samples collected during the Apollo program. These samples have special storage and handling requirements that necessitate their processing in a -20°C environment that meets the Apollo materials and cleanliness requirements. NASA has recently undertaken the development and implementation of a cold sample processing facility to support ANGSA. A similar facility will be needed to process the cold, volatile-bearing samples planned to be returned by Artemis missions; therefore, ANGSA provides excellent preparation for Artemis’ future cold sample processing efforts. We will outline the goals of the ANGSA and Artemis programs, illustrating the complementary nature of the work for both. We will describe the efforts to date in designing, testing, and implementing a cold curation facility that meets the requirements of ANGSA and Apollo curation. We will then outline future work for that facility to reach operational readiness. Finally, we will present the sample collection and curation strategies for Artemis, showing how they overlap and build on ANGSA efforts. The development of cold curation at NASA represents a significant leap in the knowledge, experience, and technologies used in astromaterials curation, opening the door for new investigations of lunar volatiles, impacts, formation processes, prebiotic chemistry, and resource utilization, among many others.

Julie Mitchell↗

NASA NTRS2018

Preliminary Interplanetary Mission Design and Navigation for the Dragonfly New Frontiers Mission Concept

Dragonﬂy is one of two mission concepts selected in December 2017 to advance into Phase A of NASA’s New Frontiers competition. Dragonﬂy would address the Ocean Worlds mission theme by investigating Titan’s habitability and prebiotic chemistry and searching for evidence of chemical biosignatures of past (or extant) life. A rotorcraft lander, Dragonﬂy would capitalize on Titan’s dense atmosphere to enable mobility and sample materials from a variety of geologic settings. This paper describes Dragonﬂy’s baseline mission design giving a complete picture of the inherent tradespace and outlines the design process from launch to atmospheric entry.

Laipert, Frank E.↗

NASA NTRS2021

Neutral–neutral synthesis of organic molecules in cometary comae

Remote and in situ observations of cometary gases have revealed the presence of a wealth of complex organic molecules, including carbon chains, alcohols, imines, and the amino acid glycine. Such chemical complexity in cometary material implies that impacts by comets could have supplied reagents for prebiotic chemistry to young planetary surfaces. However, the assumption that some of the molecules observed in cometary comae at millimetre wavelengths originate from ices stored inside the nucleus has not yet been proven. In fact, the comae of moderately-active comets reach sufficient densities within a few thousand kilometres of the nucleus for an active (solar radiation-driven) photochemistry to ensue. Here, we present results from our latest chemical-hydrodynamic models incorporating an updated reaction network, and show that the commonly-observed HC3N (cyanoacetylene) and NH2CHO (formamide) molecules can be efficiently produced in cometary comae as a result of two-body, neutral–neutral, gas-phase reactions involving well-known coma species. In the presence of a near-nucleus distributed source of CN (similar to that observed by the Rosetta spacecraft at comet 67P), we find that sufficient HC3N and NH2CHO can be synthesized to match the abundances of these molecules observed previously in Oort cloud comets. The precise coma origins of these (and other) complex organic molecules can be verified through radio interferometric mapping observations, for example using the Atacama Large Millimeter/submillimeter Array.

Comets↗

NASA NTRSDate not supplied

Mars Commercial-Compatible Initial Human-Precursor Surveying and Instrument-Deployment Concepts

Water is a critical resource need for future human exploration and habitation of Mars and other planetary environments. An integral scientific question in the search for life outside of Earth is: What are the constraints on life in planetary environments? One of the most critical features of habitable environments is the availability of water - both as an environment for prebiotic chemistry, abiogenesis, and life; and as a vehicle for generating geo- and electro- chemical systems that can support metabolism. Seeking evidence of life prior to human arrival is important both to preserve signs of any existing or past evidence of Martian life, reducing the risks of unintentional forward contamination of Martian environments, and to potentially protect the health of any human crews. Looking forward towards Mars, future human exploration will require a rapid, but thorough, initial survey of any local “area of operations” on Mars to determine the spatial distribution, quantity, and quality (e.g., salt/mineral/organic content) of any local water, as well as to evaluate any signs of current or extinct life. We will discuss several candidate field survey methodologies, involving humans, a teamed instrument platform and a surveying/sampling rover. These are proposed to be validated in a given terrestrial Mars analog environment exhibiting varying distributions of water (ice, permafrost, rock-bound) to evaluate the constraints on life. Commercial space exploration brings the future possibility of unprecedented mass, power and in situ instrument capability, potentially enabling thorough exploration of the geology, hydrology and astrobiology of a km-radius study-zone around a future Mars human/commercial space landing site. We propose to study several representative planetary surface precursor-survey architectures and mission concepts (that are commercial-Mars-compatible), and to test and compare them in field application. We will examine some of the performance issues, using given metrics and controls, of spacesuited humans using handheld and standalone instruments, vs. a robotic human-tended rover/drill, robot arm and instruments. The latter rover-based architecture can in turn be viewed in terms of returned-to-base sample in-situ analyses vs sample analysis performed on a standalone instrument platform deployed away from the primary area of operations.

astrobiology↗

NASA NTRSDate not supplied

“Are We There Yet?” Can We Biomap the Solar System with Low-Cost Solar Sail Missions?

Abstract: So much of our effort in space exploration has been devoted to one-off missions with major investments in each. This is a great strategy for early investigations of clearly significant planetary and small body destinations, but we have an entire Solar System to interrogate and the pace has definitely been slow to date. We are in the dawning era of much smaller spacecraft, and the potential to gather data from multiple destinations over longer time spans with a heightened cadence of missions to allow us to conduct survey-style investigations of the vast number of objects that attend our particular star. If we think of solar systems as belonging to one of two classes, i.e. life-bearing or not life-bearing, then the presence of some sort of biological or prebiological phenomenon on any individual body in a system places that system in the first category. The emergence of life can then be considered as a solar system-wide property and the entire suite of ingredients and processes that go into kindling of life anywhere within that system is of interest. This ranges from bodies with prebiotic chemistry through to full-blown biospheres. Thus, all bodies in a solar system are part of the milieu within which life occurs. Can the idea of low-cost solar sail-propelled spacecraft deployed en masse be useful for something as hard to investigate as life-like phenomena and their precursors? Perhaps, the answer is yes, and we must give serious attention to the possibilities.

Penelope J Boston↗

NASA NTRS2022

Rapid Radiolytic Degradation of Amino Acids in the Martian Shallow Subsurface: Implications for the Search for Extinct Life

Amino acids are fundamental to life as we know them as the monomers of proteins and enzymes. They are also readily synthesized under a variety of plausible prebiotic conditions and are common in carbon-rich meteorites. Thus, they represent a reasonable class of organics to target in the search for prebiotic chemistry or chemical evidence of life on Mars. However, regardless of their origin, amino acids and other organic molecules present in near-surface regolith and rocks on Mars can be degraded by exposure to cosmic rays that can penetrate to a depth of a few meters. We exposed several pure amino acids in dry and hydrated silicate mixtures and in mixtures of silicates with perchlorate salts to gamma radiation at various temperatures and radiation doses representative of the martian near-subsurface. We found that irradiation of amino acids mixed with dry silica powder increased the rate of amino acid radiolysis, with the radiolysis constants of amino acids in silicate mixtures at least a factor of 10 larger compared with the radiolysis constants of amino acids alone. The addition of perchlorate salts to the silicate samples or hydration of silicate samples further accelerated the rate of amino acid destruction during irradiation and increased the radiolysis constants by a factor of *1.5. Our results suggest that even low-molecular-weight amino acids could degrade in just *20 million years in the top 10 cm of the martian surface regolith and rock, and even faster if the material contains elevated abundances of hydrated silicate minerals or perchlorates. We did not detect evidence of amino acid racemization after gamma radiation exposure of the samples, which indicates that the chirality of some surviving amino acids may still be preserved. Our experimental results suggest serious challenges for the search of ancient amino acids and other potential organic biosignatures in the top 2 m of the martian surface.

Alexander A. Pavlov↗

NASA NTRS2022

Extreme Energetic Particle Events By Superflare-Associated CMES From Solar-Like Stars

Discovery of frequent superflares on active cool stars opened a new avenue in understanding the properties of eruptive events and their impact on exoplanetary environments. Solar data suggest that coronal mass ejections (CMEs) should be associated with superflares on active solar-like planet hosts and produce solar/stellar energetic particle (SEP/StEP) events. Here, we apply the 2D Particle Acceleration and Transport in the Heliosphere model to simulate the SEPs accelerated via CME-driven shocks from the Sun and young solar-like stars. We derive the scaling of SEP fluence and hardness of energy spectra with CME speed and associated flare energy. These results have crucial implications for the prebiotic chemistry and expected atmospheric biosignatures from young rocky exoplanets as well as the chemistry and isotopic composition of circumstellar disks around infant solar-like stars.

Junxiang Hu↗

NASA NTRSDate not supplied

Technology Development of a Solid State 266 nm Laser for NASA’s Dragonfly Mission

NASA’s Dragonfly mission is a rotorcraft lander which will explore several geologic locations on Saturn’s moon, Titan and investigate evidence of surface-level prebiotic chemistry as well as search for chemical signatures of water-based and/or hydrocarbon-based life. To perform molecular composition investigations in-situ, the payload includes the Dragonfly Mass Spectrometer (DraMS), being developed at NASA’s Goddard Space Flight Center (GSFC). DraMS will utilize laser desorption mass spectrometry (LDMS) to interrogate surface samples and measure the organic composition. Enabling this science capability is the Throttled Hydrocarbon Analysis by Nanosecond Optical Source (THANOS) laser being developed at NASA-GSFC. The THANOS laser is comprised of a solid state, passively Q-Switched Nd:YAG oscillator which is frequency converted to 266 nm and utilizes a RTP high voltage electro-optic for pulse energy control. The laser outputs <2.0 ns pulses with a maximum energy of approximately 200 uJ which can be emitted in 1 - 50 shot bursts at 100 Hz while performing LDMS science operations. While operating, the laser has the capability to throttle its UV pulse energy output from full attenuation to maximum energy to provide varying levels of fluence on samples in the DraMS instrument. This paper reports the technology development and space qualification effort of the THANOS laser including vibration, thermal vacuum cycling, radiation as well as Titan atmospheric composition optical damage testing performed at NASA-GSFC from 2019 through 2022.

Matthew W Mullin↗

NASA NTRS2022

A Primordial Atmospheric Origin of Hydrospheric Deuterium Enrichment on Mars

The deuterium-to-hydrogen (D/H or 2H/1H) ratio of Martian atmospheric water (~6× standard mean ocean water, SMOW) is higher than that of known sources, requiring planetary enrichment. A recent measurement by NASA’s Mars Science Laboratory rover Curiosity of Hesperian-era (>3 Ga) clays yields a D/H ratio ~3×SMOW, demonstrating that most of the enrichment occurs early in Mars’s history, reinforcing the conclusions of Martian meteorite studies. As on Venus, Mars’s D/H enrichment is widely thought to reflect preferential loss to space of 1H (protium) relative to 2H (deuterium), but both the cause and the global environmental context of large and early hydrogen losses remain to be determined. Here, we apply a recent model of primordial atmosphere evolution to Mars, link the magma ocean of the accretion epoch with a subsequent water-ocean epoch, and calculate the behavior of deuterium for comparison with the observed record. In contrast to earlier works that consider Martian D/H fractionation in atmospheres in which hydrogen reservoirs are present exclusively as H2O or H2, here we consider 2-component (H2O-H2) outgassed atmospheres in which both condensed (H2O) and escaping (H2) components – and their interaction – are explicitly calculated. We find that a a ≈2-3× hydrospheric deuterium-enrichment is produced rapidly if the Martian magma ocean is chemically reducing at last equilibration with the primordial atmosphere, making H2 and CO the initially dominant species, with minor abundances of H2O and CO2. Reducing gases – in particular H2 – can cause substantial greenhouse warming and prevent a water ocean from freezing immediately after the magma ocean epoch. We find that greenhouse warming due to plausible H2 inventories (pH2=1-102 bars) yields surface temperatures high enough (Ts=290-560 K) to stabilize a water ocean and produce an early hydrological cycle through which surface water can be circulated. Moreover, the pressure-temperature conditions are high enough to produce ocean-atmosphere H2O-H2 isotopic equilibrium through gas-phase deuterium exchange such that surface H2O strongly concentrates deuterium relative to H2, which preferentially takes up protium and escapes from the primordial atmosphere. The efficient physical separation of deuterium-rich (H2O) and deuterium-poor (H2) species via condensation permits equilibrium isotopic partitioning and early atmospheric escape to be recorded in modern crustal reservoirs. The proposed scenario of primordial H2-CO-rich outgassing and escape suggests significant durations (>Myr) of chemical conditions on the Martian surface conducive to prebiotic chemistry immediately following magma ocean crystallization.

Mars↗

NASA NTRSDate not supplied

Dragonfly Preparation for Powered Flight: Lander Separation State Control to Ensure Successful Landing

NASA’s Dragonfly mission, led by The Johns Hopkins University Applied Physics Laboratory, is a relocatable octocopter lander to study Saturn’s largest moon Titan. The scientific goals of the mission include studying Titan’s prebiotic chemistry, geology, and atmosphere. Upon Titan arrival, the lander will enter the atmosphere, descend on a parachute to a ground-relative altitude of about 1000 m before being released, and then fly on internal power down to the surface. To guarantee desirable initial conditions for the lander release, the lander must meet certain angular rate conditions. These conditions include reducing the spin rate about the vertical axis to 4.9 deg/sec, using the rotors as actuators; and releasing with a negative pitch rate (rotating nose down) to ensure a successful transition to powered flight. This is achieved using a release trigger. Achieving these desired rates for lander release is part of the mission phase known as ‘preparation for powered flight’ (PPF). This paper proposes controls and logic to achieve the desired conditions for releasing the lander from the parachute.

Flight Mechanics↗

NASA NTRSDate not supplied

Dragonfly Preparation for Powered Flight: Lander Separation State Control to Ensure Successful Landing

Flight Mechanics↗

NASA NTRSDate not supplied

Performance of the Dragonfly Mass Spectrometer (DraMS) Programmable UV Laser Source Engineering Test Unit (ETU)

NASA’s Dragonfly mission will sample surface materials from multiple sites on Saturn’s largest moon, Titan, in exploration of its potential for prebiotic chemistry. We report on the performance of our short-pulsed UV laser transmitter, developed for the Dragonfly’s on-board Mass Spectrometer (DraMS). Our engineering test unit (ETU) has completed flight qualification and demonstrated its operational science requirements, such that the final flight unit build can begin. The Titan Hydrocarbon Analysis Nanosecond Optical Source (THANOS) ETU laser produces 266 nm laser pulses at programmable energy levels in order to create high resolution laser desorption mass spectrometry (LDMS) measurements. The laser operates in short bursts of 1-50 pulses, each at < 2 ns pulse width, at a 100 Hz repetition rate. Creating a sealed Titanium unit, capable of operation on the extreme environment of Titan’s surface was a major engineering challenge. The laser successfully demonstrated its ability to meet all operational requirements in terms of pulse energy, beam pointing on target and repeatability even after extensive environmental testing.

Matthew W Mullin↗

NASA NTRSDate not supplied

Performance of the Dragonfly Mass Spectrometer (DraMS) Programmable UV Laser Source Engineering Test Unit (ETU)

Matthew Mullin↗

NASA NTRS2023

Evaluation of the Interference of Tenax®TA Adsorbent With Dimethylformamide Dimethyl Acetal Reagent for Gas Chromatography-Dragonfly Mass Spectrometry and Future Gas Chromatography-Mass Spectrometry in Situ Analysis

Among future space missions, national aeronautics and space administration (NASA) selected two of them to analyze the diversity in organic content within Martian and Titan soil samples using a gas chromatograph – mass spectrometer (GC–MS) instrument. The Dragonfly space mission is planned to be launched in 2027 to Titan's surface and explore the Shangri-La surface region for years. One of the main goals of this mission is to understand the past and actual abundant prebiotic chemistry on Titan, which is not well characterized yet. The ExoMars space mission is planned to be launched in 2028 to Mars’ surface and explore the Oxia Planum and Mawrth Vallis region for years. The main objectives focus on the exploration of the subsurface soil samples, potentially richer in organics, that might be relevant for the search of past life traces on Mars where irradiation does not impact the matrices and organics. One recently used sample pre-treatment for gas chromatography – mass spectrometry analysis is planned on both space missions to detect refractory organic molecules of interest for astrobiology. This pre-treatment is called derivatization and uses a chemical reagent – called dimethylformamide dimethyl acetal (DMF-DMA) – to sublimate organic compounds keeping them safe from thermal degradation and conserving the chirality of the molecules extracted from Titan or Mars’ matrices. Indeed, the detection of building blocks of life or enantiomeric excess of some organics (e.g. amino acids) after DMF-DMA pre-treatment and GC–MS analyses would be both bioindicators. The main results highlighted by our work on DMF-DMA and Tenax®TA interaction and efficiency to detect organic compounds at ppb levels in a fast and single preparation are first that Tenax®TA did not show the onset of degradation until after 150 experiments – a 120 h at 300 °C experiment – which greatly exceeds the experimental lifetimes for the DraMS and GC-space in situ investigations. Tenax®TA polymer and DMF-DMA produce many by-products (about 70 and 46, respectively, depending on the activation temperature). Further, the interaction between the two leads to the production of 22 additional by-products from DMF-DMA degradation, but these listed by-products do not prevent the detection of trace-level organic molecules after their efficient derivatization and volatilization by DMF-DMA in the oven ahead the GC–MS trap and column.

DraMS-Dragonfly mission↗

NASA NTRS1986

Clay energetics in chemical evolution

Clays have been implicated in the origin of terrestrial life since the 1950's. Originally they were considered agents which aid in selecting, concentrating and promoting oligomerization of the organic monomeric substituents of cellular life forms. However, more recently, it has been suggested that minerals, with particular emphasis on clays, may have played a yet more fundamental role. It has been suggested that clays are prototypic life forms in themselves and that they served as a template which directed the self-assembly of cellular life. If the clay-life theory is to have other than conceptual credibility, clays must be shown by experiment to execute the operations of cellular life, not only individually, but also in a sufficiently concerted manner as to produce some semblance of the functional attributes of living cells. Current studies are focussed on the ability of clays to absorb, store and transfer energy under plausible prebiotic conditions and to use this energy to drive chemistry of prebiotic relevance. Conclusions of the work are applicable to the role of clays either as substrates for organic chemistry, or in fueling their own life-mimetic processes.

Coyne, L. M.↗