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NASA NTRSDate not supplied

Rotational Spectroscopy is SubLIME: Site-Specific Identification of Compounds Formed on UV-photolyzed Cosmcs Ice

A variety of organic compounds has been detected in comets, meteorites, and the cold gas enveloping infant stars. These compounds display a range of complexity and include so-called complex organic molecules that may have astrobiological implications. Laboratory studies of photolyzed and nonirradiated interstellar, planetary, and cometary ices have demonstrated many astrochemical formation routes and require sensitive analytical techniques to identify the composition of ice and gas products formed. The unique identification of organics can be challenging and often requires structure-specific techniques to identify structural isomers, conformers, and isotopologues. We present the approaches used in SubLIME, the Sublimation of Laboratory Ices Millimeter/submillimeter Experiment, which uses the structure-specificity of rotational spectroscopy to identify the composition and abundances of sublimated products of UV-photolyzed ice samples. Ices are formed and photolyzed at low temperature (~10 K) and slowly heated to 300 K to sublimate the volatile products. The gas mixture is then investigated with millimeter/submillimeter spectroscopy, and the resulting spectra compared to observational spectra collected with submillimeter/far-IR telescopes. We present the experimental set-up and results of UV-photolyzed interstellar ice analogues containing water (H O) and carbon monoxide (CO). Formation routes for identified molecules are proposed for follow-up experimental and theoretical investigations.

Olivia H. Wilkins↗
NASA NTRS1992

Infrared imaging of Mars for volatile distribution and seasonal variability between 2.4 and 5.1 microns

Recent advances in ground-based infrared imaging now allow for sub-arc second spectral imaging. Data collected at the NASA Infrared Telescope Facility using protocam, a 62 x 58 InSb array camera with a circular variable filter and a plate scale 0.2 arc-seconds/pixel, are discussed. These images are a first attempt at extended seasonal infrared coverage of Mars to look for seasonal variations. Currently, data collected in Jun. 1990 at Ls = 241 (southern spring) and in Jan. 1991 Ls = 360 (late southern summer) are being reduced and analyzed. The 3 micron bound water band is the strongest surface absorption feature on Mars in the infrared. Infrared spectroscopy can also be useful in the detection of ice and frost deposits, especially in the polar regions. While imaging and spectroscopy at visible wavelengths allows for the detection of condensates, infrared information is needed to distinguish between water and CO2 ice/frost deposits. In the Jun. images, the southern polar cap totally disappears in the 3.4 micron CO2 frost band and is bright in the 3.1 micron water ice band, indicating that water ice is not a detectable component of the southern polar cap at this season. Further investigations are currently under way to look for residual water ice after the disappearance of the seasonal south polar cap in the Jan. images. The Jun. images that were focused on had a sub-earth point located at 184 longitude, and 23.8 S latitude which put the center of the disk in the southern highland region between Elysium and Amazonis. Examination of the Jun. images show that there are four surface units identifiable: a CO2 frost deposit, a northern plains unit, an equatorial unit, and a southern highland unit. At this resolution there does not appear to be any latitudinal variations in the 3 micron band that is independent of the 2.4 micron albedo features. The northern planes unit and the southern highland unit have very similar 'color' in the three micron band as demonstrated by the rise out of the band, but different brightness levels. The equatorial unit has a distinct three micron color implying a compositional difference. The albedo features at 2.4 microns have decreased contrast at longer wavelengths, till they are unrecognizable at 4 microns.

Blaney, Diana L.↗
NASA NTRS2018

Polar Volatiles Exploration in Peary Crater Enabled by NASA's Kilopower Project

For more than 50 years, scientists have discussed the possibility of the existence of water ice and other frozen volatiles at the lunar poles [1]. However, it was not until the 1990s when the polar orbiting spacecraft Clementine and Lunar Prospector collected data supporting these hypotheses [2]. Subsequent missions, including the Lunar Reconnaissance Orbiter (LRO) mission [3], and the Lunar Crater Observation and Sensing Satellite (LCROSS) mission [4], provided further evidence that supports the existence of water ice deposits at the lunar poles. During NASA's Constellation Program, several areas at both lunar poles polar were included in 50 Regions of Interest (ROI) for intensive study by the Lunar Reconnaissance Orbiter Camera (LROC) [5]. These polar ROI focused on peaks and craters rims that received high amounts of solar illumination, assuming initial missions back to the lunar surface would utilize solar arrays to generate electricity. Recently, the successful demonstration of NASA's Kilopower Project at the National Nuclear Security Administration (NNSA) Nevada National Security Site makes it possible to consider lunar polar missions at locations other than highly illuminated regions. The Kilopower Project was initiated in 2015 to demonstrate subsystem-level technology readiness of a small space fission power system [6]. This abstract describes the science objectives and operations for a mission concept developed at NASA Glenn Research Center's COMPASS Concurrent Engineering Team for a 1-year exploration of Peary Crater focused on prospecting for lunar polar volatiles.

Gruener, J. E.↗
NASA NTRS2016

The Chlorine Isotopic Composition Of Lunar UrKREEP

Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. Numerous studies have examined the abundances and isotopic compositions of volatiles in lunar apatite, Ca5(PO4)3(F,Cl,OH). In particular, apatite has been used as a tool for assessing the sources of H2O in the lunar interior. However, current models for the Moon's formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. For ex-ample, in the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs (Rare Earth Elements), and P, collectively called KREEP, and in its primitive form - urKREEP, given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon (BSM). In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes in lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

Barnes, J. J.↗
NASA NTRS1992

SIMS chemical analysis of extended impact features from the trailing edge portion of experiment AO187-2

One hundred capture cells from the trailing edge, which had lost their cover foils during flight, were optically scanned for extended impact features caused by high velocity projectiles impinging on the cells while the foils were still intact. Of the 53 candidates, 24 impacts were analyzed by secondary ion mass spectroscopy for the chemical composition of the deposits. Projectile material was found in all impacts, and at least 75 percent of them appear to be caused by interplanetary dust particles. Elemental ratios are fractionated, with refractory elements enriched in the impacts relative to interplanetary dust particles collected in the stratosphere. Although this could be due to systematic differences in the compositions, a more likely explanation is volatility fractionation during the impact process.

Amari, Sachiko↗
NASA NTRS1998

Thermal and evolved gas analyzer

The Thermal and Evolved Gas Analyzer (TEGA) instrument will perform calorimetry and evolved gas analysis on soil samples collected from the Martian surface. TEGA is one of three instruments, along with a robotic arm, that form the Mars Volatile and Climate Survey (MVACS) payload. The other instruments are a stereo surface imager, built by Peter Smith of the University of Arizona and a meteorological station, built by JPL. The MVACS lander will investigate a Martian landing site at approximately 70 deg south latitude. Launch will take place from Kennedy Space Center in January, 1999. The TEGA project started in February, 1996. In the intervening 24 months, a flight instrument concept has been designed, prototyped, built as an engineering model and flight model, and tested. The instrument performs laboratory-quality differential-scanning calorimetry (DSC) over the temperature range of Mars ambient to 1400K. Low-temperature volatiles (water and carbon dioxide ices) and the carbonates will be analyzed in this temperature range. Carbonates melt and evolve carbon dioxide at temperatures above 600 C. Evolved oxygen (down to a concentration of 1 ppm) is detected, and C02 and water vapor and the isotopic variations of C02 and water vapor are detected and their concentrations measured. The isotopic composition provides important tests of the theory of solar system formation.

Williams, M. S.↗
NASA NTRS2013

Cryogenic Curation: Isolated Technology and Mission Operational Requirements for Sample Return

Future lunar, Mars, asteroid, and comet sample return missions may collect samples that have been preserved at sub-freezing or even cryogenic temperatures. For such samples, the study of volatiles and temperature-sensitive minerals will have high priority. Valuable geochemical and mineralogical information will be lost if such samples are allowed to reach ambient temperatures on Earth. The ability to store, document, subdivide, and transport extraterrestrial geologic samples while maintaining sub-freezing or cryogenic temperatures, possibly as low as 40 K, is required for the complete scientific study of samples from cold environments.

Calaway, Michael J.↗
NASA NTRS1994

ASTM E 1559 method for measuring material outgassing/deposition kinetics has applications to aerospace, electronics, and semiconductor industries

The American Society for Testing and Materials has published a new standard test method for characterizing time and temperature-dependence of material outgassing kinetics and the deposition kinetics of outgassed species on surfaces at various temperatures. This new ASTM standard, E 1559(1), uses the quartz crystal microbalance (QCM) collection measurement approach. The test method was originally developed under a program sponsored by the United States Air Force Materials Laboratory (AFML) to create a standard test method for obtaining outgassing and deposition kinetics data for spacecraft materials. Standardization by ASTM recognizes that the method has applications beyond aerospace. In particular, the method will provide data of use to the electronics, semiconductor, and high vacuum industries. In ASTM E 1559 the material sample is held in vacuum in a temperature-controlled effusion cell, while its outgassing flux impinges on several QCM's which view the orifice of the effusion cell. Sample isothermal total mass loss (TML) is measured as a function of time from the mass collected on one of the QCM's which is cooled by liquid nitrogen, and the view factor from this QCM to the cell. The amount of outgassed volatile condensable material (VCM) on surfaces at higher temperatures is measured as a function of time during the isothermal outgassing test by controlling the temperatures of the remaining QCM's to selected values. The VCM on surfaces at temperatures in between those of the collector QCM's is determined at the end of the isothermal test by heating the QCM's at a controlled rate and measuring the mass loss from the end of the QCM's as a function of time and temperature. This reevaporation of the deposit collected on the QCM's is referred to as QCM thermogravimetric analysis. Isothermal outgassing and deposition rates can be determined by differentiating the isothermal TML and VCM data, respectively, while the evaporation rates of the species can be obtained as a function of temperature by differentiating the QCM thermogravimetric analysis data.

Garrett, J. W.↗
NASA NTRS1973

Interstellar grains in museums

It is argued that carbonaceous chondrites, particularly of type I, are probably collections of interstellar grains which have been mildly transformed through exposure to higher than normal temperatures, resulting in a loss of volatile materials.

Cameron, A. G. W.↗
NASA NTRS1985

Scientific objectives for a 1996 Mars Sample Return Mission

The Mars Sample Return Mission, designed to return a variety of surface and subsurface samples as well as atmospheric samples, is described. Primary information about the planet is essential to understanding its place in the evolution of the solar system. The most accurate landing techniques will be used to place the lander near geologically interesting features. A capable rover will be an essential element of the sample collection strategy to maximize the diversity of the samples. The sample collection and return systems will keep the samples at Mars ambient conditions or colder to preserve the abundances and distribution of volatile components. Planetary quarantine is an important consideration for both the Mars lander and the earth return vehicle. Quarantine procedures must be consistent with the primary objectives of the mission and must not compromise the investigations of the returned samples.

Blanchard, D. P.↗
NASA NTRS2000

Thermal and Evolved Gas Analysis of Hydromagnesite and Nesquehonite: Implications for Remote Thermal Analysis on Mars

Volatile-bearing minerals (e.g., Fe-oxyhydroxides, phyllosilicates, carbonates, and sulfates) may be important phases on the surface of Mars. In order to characterize these potential phases the Thermal Evolved-Gas Analyzer (TEGA), which was onboard the Mars Polar Lander, was to have performed differential scanning calorimetry (DSC) and evolved-gas analysis of soil samples collected from the surface. The sample chamber in TEGA operates at about 100 mbar (approximately 76 torr) with a N2, carrier gas flow of 0.4 seem. Essentially, no information exists on the effects of reduced pressure on the thermal properties of volatile-bearing minerals. In support of TEGA, we have constructed a laboratory analog for TEGA from commercial instrumentation. We connected together a commercial differential scanning calorimeter, a quadruple mass spectrometer, a vacuum pump, digital pressure gauge, electronic mass flow meter, gas "K" bottles, gas dryers, and high and low pressure regulators using a collection of shut off and needle valves. Our arrangement allows us to vary and control the pressure and carrier gas flow rate inside the calorimeter oven chamber.

Lauer, H. V., Jr.↗
NASA NTRSDate not supplied

Petrologic Comparison of High- and Low-Titanium Basalt Clasts Derived From ANGSA Core 73001

Volatile elements and compounds significantly influence the properties and behavior of magma, including ascent and eruptive processes. Basalts record a complicated history of the volatile species inherent to their parental magma, and the processes, such as degassing, that change these volatile inventories. On the Moon, outstanding questions remain concerning the behavior of magmatic volatiles and their roles in the evolution of lunar magmas and the formation of mare basalts. As part of the Apollo Next Generation Sample Analysis (ANGSA) program, we are investigating the petrogenesis of two basalt clasts collected from the recently processed Apollo 17 drive tube, 73001. Our team is studying the petrology of the two basalt clasts in 2D and 3D. Recent work has highlighted the utility of coupling traditional 2D methods with 3D measurements to better understand the crystallization and degassing histories of lunar lava flows. We are also investigating the volatile inventory of the samples through in situ studies of volatile-bearing phases, like apatite, to understand the eruptive signatures and degassing histories of low-titanium and high-titanium lunar basalts. At the upcoming conference, we will present the first detailed study of the 2D and 3D mineralogy, textures, 3D vesiculation, and chemistry of these basalt clasts to shed light on their magmatic, volcanic, and post-eruptive histories.

Basalt↗
NASA NTRS2015

Advanced Curation: Solving Current and Future Sample Return Problems

Advanced Curation is a wide-ranging and comprehensive research and development effort at NASA Johnson Space Center that identifies and remediates sample related issues. For current collections, Advanced Curation investigates new cleaning, verification, and analytical techniques to assess their suitability for improving curation processes. Specific needs are also assessed for future sample return missions. For each need, a written plan is drawn up to achieve the requirement. The plan draws while upon current Curation practices, input from Curators, the analytical expertise of the Astromaterials Research and Exploration Science (ARES) team, and suitable standards maintained by ISO, IEST, NIST and other institutions. Additionally, new technologies are adopted on the bases of need and availability. Implementation plans are tested using customized trial programs with statistically robust courses of measurement, and are iterated if necessary until an implementable protocol is established. Upcoming and potential NASA missions such as OSIRIS-REx, the Asteroid Retrieval Mission (ARM), sample return missions in the New Frontiers program, and Mars sample return (MSR) all feature new difficulties and specialized sample handling requirements. The Mars 2020 mission in particular poses a suite of challenges since the mission will cache martian samples for possible return to Earth. In anticipation of future MSR, the following problems are among those under investigation: What is the most efficient means to achieve the less than 1.0 ng/sq cm total organic carbon (TOC) cleanliness required for all sample handling hardware? How do we maintain and verify cleanliness at this level? The Mars 2020 Organic Contamination Panel (OCP) predicts that organic carbon, if present, will be present at the "one to tens" of ppb level in martian near-surface samples. The same samples will likely contain wt% perchlorate salts, or approximately 1,000,000x as much perchlorate oxidizer as organic carbon. The chemical kinetics of this reaction are poorly understood at present under the conditions of cached or curated martian samples. Among other parameters, what is the maximum temperature allowed during storage in order to preserve native martian organic compounds for analysis? What is the best means to collect headspace gases from cached martian (and other) samples? This gas will contain not only martian atmosphere but also off-gassed volatiles from the cached solids.

Fries, M.↗
NASA NTRS2020

Advanced Curation of Astromaterials for Planetary Science Over the Next Decade

Advanced curation is a cross-disciplinary field of research and development aiming to improve curation and sample acquisition practices in existing astromaterials collections and to enable future sample return activities.The primary result of advanced curation is to both reduce and quantify contamination to astromaterials and preserve the scientific integrity of all samples from mission inception to scientific analysis. Over the next decade, NASA should support advanced curation research and monitoring efforts as they pertain to improving our current collections and preparing for samples from current and future astromaterials acquisition activities.We highlight here five advanced curation activities of critical importance for the success of sample science supported by NASA over the coming decade, including: 1) supporting efforts to build contamination knowledge collections as part of sample return missions, which requires curation involvement from the earliest stages of sample return mission planning;2) supporting Earth-based astromaterials collection campaigns of meteorites and cosmic dust as they represent relatively inexpensive sample acquisition activities that continue to grow NASA’s astromaterials collections and enable new discoveries;3) preparing to curate and process samples under “cold” conditions to enable return of samples from volatile-rich Solar System targets like permanently shadowed regions on the lunar surface orcomets;4) determining how best to combine clean room technology and biosafety technology into one infrastructure to support curation of samples from bodies designated as Category V:Restricted Earth Return; and 5) supporting real-time monitoring and testing of curation labs to verify that sample processing environments remain clean from the standpoint of inorganic, organic, and biological contamination

Francis M. McCubbin↗
NASA NTRSDate not supplied

Predicting the Seawater Chemistry of an Ocean World Using Machine Learning on Isotopic Measurements of Volatile CO2

Introduction: Given the long time intervals required for data transmission to and from ocean worlds targets, low bandwidth for data transmission, time required for data processing and analysis, and potentially extreme radiation environments (e.g., Europa), it is clear that ocean worlds missions will need more autonomous flight instruments and software in order to achieve established science goals. Protracted time intervals for data analysis (e.g., Europa Lander) strongly motivates the development of rapid, consistent and streamlined methods for interpreting data from flight mass spectrometers to e.g., determine how mass spectra from a plume or surface liquid/ice relates to the surface/subsurface. Since mass spectrometry also has the potential to correctly identify biosignatures[1], it is imperative that such methods for interpreting data are consistent and accurate. We used 848 isotope ratio mass spectra from laboratory analyses of CO2 that interacted with ocean worlds-relevant seawaters as a ‘training’ dataset for ‘unsupervised’ machine learning. In unsupervised learning, characteristics of the data are not labeled or linked, and any similarities found only result from the neural network. CO2 isotopologues analyzed for this dataset mimic the remote measurements of CO2 by a flight mass spectrometer, and are detailed in Theiling [2]. From this dataset, we used measured features of the spectra, such as retention time, intensity, and (isotopologue) mass ratios as inputs for our autoencoder neural network. Our neural network was trained to find similarities in these and other spectral features for seawaters of a particular composition and amount of initial CO2. Successful training then created an output of these similarities for various seawaters, which included MgSO4, Na2SO4, NaCl, MgCl2, KCl, and NaHCO3, and combinations of these salts. We then applied dimensionality reduction techniques such as Principal Component Analysis (PCA), T-Distributed Stochastic Neighbor Embedding (TSNE), and Uniform Manifold Approximation and Projection (UMAP) to demonstrate latent data features as a two-dimensional projection in a unitless, high-dimensional space. In this projection, a data point represents the combined effect of spectral features such as intensity, retention time, and isotope ratio. Our initial UMAP demonstrates data clustering (organization of the data by the neural network) based on the amount of CO2 that had initially interacted with each seawater. Further training using more ‘supervised’ learning techniques demonstrate strong clustering of preliminary data based on initial CO2 concentration, seawater chemical composition, and ionic strength (salinity). Our preliminary work therefore suggests that machine learning has the potential to identify compositional variants of an ocean world seawater based on mass spectra from volatile CO2 measurements. Acknowledgments: This work was funded through a Strategic Task Group at NASA Goddard Space Flight Center. The training dataset was collected through funding from the Oklahoma Space Grant Consortium. References: [1] Pappalardo, R. et al. (2013) Astrobiology, 13, 740–773. [2] Theiling (2020) Icarus, 114216.

Europa↗
NASA NTRS2020

Impact-driven mobilization of deep crustal brines on dwarf planet Ceres

Ceres, the only dwarf planet in the inner Solar System, appears to be a relict ocean world. Data collected by NASA's Dawn spacecraft provided evidence that global aqueous alteration within Ceres resulted in a chemically evolved body that remains volatile-rich(1). Recent emplacement of bright deposits sourced from brines attests to Ceres being a persistently geologically active world(2,3), but the surprising longevity of this activity at the 92-km Occator crater has yet to be explained. Here, we use new high-resolution Dawn gravity data to study the subsurface architecture of the region surrounding Occator crater, which hosts extensive young bright carbonate deposits (faculae). Gravity data and thermal modelling imply an extensive deep brine reservoir beneath Occator, which we argue could have been mobilized by the heating and deep fracturing associated with the Occator impact, leading to long-lived extrusion of brines and formation of the faculae. Moreover, we find that pre-existing tectonic cracks may provide pathways for deep brines to migrate within the crust, extending the regions affected by impacts and creating compositional heterogeneity. The long-lived hydrological system resulting from the impact might also occur for large impacts in icy moons, with implications for creation of transient habitable niches over time.High-resolution data of Ceres's bright spots (faculae), obtained by Dawn's second extended mission, suggest the existence of a deep brine-rich reservoir that emerged to the surface through long-lived cryovolcanic activity as a consequence of the impact that created Occator crater.

C. A. Raymond↗
NASA NTRS2019

Lunar Ice Cube: ongoing development of first generation deep space cubesat mission with compact broadband IR spectrometer

Lunar Ice Cube (LIC) is one of 13 6U cubesats that will be deployed by EM1 in cislunar space. LIC along with Lunar Flashlight and LunaH-Map, all focused on the search for volatiles but with very different payloads, will be the first deep space cubesats designed to address goals for both demonstrating new technologies and collecting scientific data. Effectively, as their developments are occurring in parallel, they are acting as prototypes for future deep space cubesats missions. One useful outcome of this experiment is to evolve a working paradigm for the development and operation of compact, cost-capped, standardized (supporting subsystems) spacecraft to serve the needs of diverse user communities.

Mason, Paul↗
NASA NTRS2017

Chlorine in Lunar Basalts

In the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs, and P, collectively called KREEP, and in its primitive form - urKREEP, [1]), given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO (e.g., [2]). When compared to chondritic meteorites and terrestrial rocks (e.g., [3-4]), lunar samples often display heavy chlorine isotope compositions [5-9]. Boyce et al. [8] found a correlation between delta Cl-37 (sub Ap) and bulk-rock incompatible trace elements (ITEs) in lunar basalts, and used this to propose that early degassing of Cl (likely as metal chlorides) from the LMO led to progressive enrichment in remaining LMO melt in Cl-37over Cl-35- the early degassing model. Barnes et al. [9] suggested that relatively late degassing of chlorine from urKREEP (to yield delta Cl-37 (sub urKREEP greater than +25 per mille) followed by variable mixing between KREEPy melts and mantle cumulates (characterized by delta Cl-37~0 per mille) could explain the majority of Cl isotope data from igneous lunar samples. In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed an in situ study of chlorine isotopes and abundances of volatiles in lunar apatite from a diverse suite of lunar basalts spanning a range of geochemical types.

Barnes, J. J.↗