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NASA NTRS2018

Overview of Primitive Object Volatile Explorer (PrOVE) CubeSat or Smallsat Concept

Here we describe the Primitive Object Volatile Explorer (PrOVE), a smallsat mission concept to study the surface structure and volatile inventory of comets in their perihelion passage phase when volatile activity is near peak. CubeSat infrastructure imposes limits on propulsion systems, which are compounded by sensitivity to the spacecraft disposal state from the launch platform and potential launch delays. We propose circumventing launch platform complications by using waypoints in space to park a deep space SmallSat or CubeSat while awaiting the opportunity to enter a trajectory to flyby a suitable target. In our Planetary Science Deep Space SmallSat Studies (PSDS3) project, we investigated scientific goals, waypoint options, potential concept of operations (ConOps) for periodic and new comets, spacecraft bus infrastructure requirements, launch platforms, and mission operations and phases. Our payload would include two low-risk instruments: a visible image (VisCAM) for 5-10 m resolution surface maps; and a highly versatile multispectral Comet CAMera (ComCAM) will measure 1) H2O, CO2, CO, and organics non-thermal fluorescence signatures in the 2-5 μm MWIR, and 2) 7-10 and 8-14 μm thermal (LWIR) emission. This payload would return unique data not obtainable from ground-based telescopes and complement data from Earth-orbiting observatories. Thus, the PrOVE mission would (1) acquire visible surface maps, (2) investigate chemical heterogeneity of a comet nucleus by quantifying volatile species abundance and changes with solar insolation, (3) map the spatial distribution of volatiles and determine any variations, and (4) determine the frequency and distribution of outbursts.

Clark, Pamela S.↗
NASA NTRS2018

Overview of Primitive Volatile Explorer (PrOVE) Cubesat or Smallsat Concept

Here we describe the Primitive Object Volatile Explorer (PrOVE), a smallsat mission concept to study the surface structure and volatile inventory of comets in their perihelion passage phase when volatile activity is near peak. CubeSat infrastructure imposes limits on propulsion systems, which are compounded by sensitivity to the spacecraft disposal state from the launch platform and potential launch delays. We propose circumventing launch platform complications by using waypoints in space to park a deep space SmallSat or CubeSat while awaiting the opportunity to enter a trajectory to flyby a suitable target. In our Planetary Science Deep Space SmallSat Studies (PSDS3) project, we investigated scientific goals, waypoint options, potential concept of operations (ConOps) for periodic and new comets, spacecraft bus infrastructure requirements, launch platforms, and mission operations and phases. Our payload would include two low-risk instruments: a visible image (VisCAM) for 5-10 m resolution surface maps; and a highly versatile multispectral Comet CAMera (ComCAM) will measure 1) H2O, CO2, CO, and organics non-thermal fluorescence signatures in the 2-5 µm MWIR, and 2) 7-10 and 8-14 µm thermal (LWIR) emission. This payload would return unique data not obtainable from ground-based telescopes and complement data from Earth-orbiting observatories. Thus, the PrOVE mission would (1) acquire visible surface maps, (2) investigate chemical heterogeneity of a comet nucleus by quantifying volatile species abundance and changes with solar insolation, (3) map the spatial distribution of volatiles and determine any variations, and (4) determine the frequency and distribution of outbursts.

Zucherman, Aaron↗
NASA NTRS1980

The contribution of cometary volatiles to the primitive earth

It has been estimated that during its early history the earth captured a mass of cometary material of the order of 10 to the 23rd grams. Since carbon is supposed to be at least three times more abundant in comets than in carbonaceous chondrites (3.5 percent C in C 1 chondrites), it can be deduced that about 1 x 10 to the 22nd grams of carbon (as carbon compounds), were added by comets to the surface of the prebiotic earth. This carbon value is of the same order of magnitude as the value of the organic carbon buried in the earth's sedimentary shell, but approximately one order of magnitude lower than the earth's surface total carbon (7 x 10 to the 22nd gm). The capture of comets by the earth would also have contributed to generating the appropriate aqueous and reducing environmental conditions necessary for organic synthesis.

Oro, J.↗
NASA NTRS1992

Environmental factors controlling fluxes of dimethyl sulfide in a New Hampshire fen

The major environmental factors controlling fluxes of dimethyl sulfide (DMS) in a Sphagnum-dominated peatland were investigated in a poor fen in New Hampshire. DMS emissions from the surface of the peatland varied greatly over 24 hours and seasonally. Maximum DMS emissions occurred in summer with minima in the late fall. Temperature was the major environmental factor controlling these variabilities. There was also some evidence that the changes in water table height might have contributed to the seasonable variability in DMS emission. The influence of the water table was greater during periods of elevated temperature. DMS and MSH were the most abundant dissolved volatile sulfur compound (VSC) in the surface of the water table. Concentrations of dissolved VSC's varied with time and space throughout the fen. Dissolved MDS, MSH, and OCS in the surface of the water table were supersaturated with respect to their concentrations in the atmosphere suggesting that the peat surface was a source of VSC's in the peatland. VCS in peatlands seemed to be produced primarily by microbial processes in the anoxic surface layers of the peat rich in organic matter and inorganic sulfide. Sphagnum mosses were not a direct source of VSC's. However, they increased transport of DMS from the peat surface to the atmosphere.

Demello, William Zamboni↗
NASA NTRS1973

Organic analysis of lunar samples and the Martian surface.

In addition to the organogenic elements (H, C, N, O, S, P) which are necessary for the synthesis of organic molecules, the lunar samples from Apollo 11, 12, 14, and 15 contain substantial amounts of CO, N2, and CO2 which are released at relatively high temperatures and smaller amounts of more complex organic compounds (e.g., benzene). The lunar surface provides one of the less favorable solar system models for the synthesis of organic compounds; yet small amounts of these compounds have been detected in the returned samples. It is reasonable to assume that the different physical and developmental features of the planet Mars (increased gravitational field, presence of an atmosphere with CO2, CO, and H2O, recent volcanic and tectonic activity, etc.) would favor an increased organic content of the surface of this planet relative to the moon. Therefore the organic molecules present in the Martian soil should be measurable by miniaturized mass spectrometers after fractional distillation or gas chromatographic separation of the volatiles released by moderate heating.

Oro, J.↗
NASA NTRS2009

Liquid Water on Enceladus from Observations of Ammonia and Ar-40 in the Plume

Jets of water ice from surface fractures near the south pole of Saturn's icy moon Enceladus produce a plume of gas and particles. The source of the jets may be a liquid water region under the ice shell-as suggested most recently by the discovery of salts in E-ring particles derived from the plume-or warm ice that is heated, causing dissociation of clathrate hydrates. Here we report that ammonia is present in the plume, along with various organic compounds, deuterium and, very probably, Ar-40. The presence of ammonia provides strong evidence for the existence of at least some liquid water, given that temperatures in excess of 180 K have been measured near the fractures from which the jets emanate. We conclude, from the overall composition of the material, that the plume derives from both a liquid reservoir (or from ice that in recent geological time has been in contact with such a reservoir) as well as from degassing, volatile-charged ice. As part of a general comprehensive review of the midsize saturnian satellites at the conclusion of the prime Cassini mission, PI McKinnon and co-I Barr contributed to three review chapters.

Waite, J. H., Jr.↗
NASA NTRS2001

Detecting Pyrolysis Products from Bacteria on Mars

A pyrolysis/sublimation technique was developed to isolate volatile amine compounds from a Mars soil analogue inoculated with approx. 10 billion Escherichia coli cells. In this technique, the inoculated soil is heated to 500 C for several seconds at Martian ambient pressure and the sublimate, collected by a cold finger, then analyzed using high performance liquid chromatography. Methylamine and ethylamine, produced from glycine and alanine decarboxylation, were the most abundant amine compounds detected after pyrolysis of the cells. A heating cycle similar to that utilized in our experiment was also used to release organic compounds from the Martian soil in the 1976 Viking gas chromatography/mass spectrometry (GC/MS) pyrolysis experiment. The Viking GC/MS did not detect any organic compounds of Martian origin above a level of a few parts per billion in the Martian surface soil. Although the Viking GC/MS instruments were not specifically designed to search for the presence of living cells on Mars, our experimental results indicate that at the part per billion level, the degradation products generated from several million bacterial cells per gram of Martian soil would not have been detected.

Glavin, Daniel↗
NASA NTRSDate not supplied

Insights Into the CM Parent Body's Interior: A Comparative Study With Bennu's Bright Boulders

CM (Mighei-like) chondrites, primitive and water-rich asteroid samples from the early solar system, are significant for their potential role in delivering water and organic compounds to Earth [1-2]. Their resemblance to near-Earth asteroids Bennu and Ryugu, the targets of recent sample return missions, highlights their importance. What we learn from CM chondrites can be applied to these intriguing celestial bodies. Initial studies indicated that phyllosilicate-rich C chondrites underwent low-temperature aqueous alteration (<150°C) [3-5]. Subsequent research revealed that some experienced post-hydration thermal metamorphism at temperatures between ∼200°C and >750°C, resulting in dehydrated minerals and reduced volatile elements [6-9].This finding challenged the previous assumption that these chondrites had not undergone significant thermal metamorphism.

I Kerraouch↗
NASA NTRS2005

Lunar and Planetary Science XXXVI, Part 13

Contents include the following: A Fast, Non-Destructive Method for Classifying Ordinary Chondrite Falls Using Density and Magnetic Susceptibility. An Update on Results from the Magnetic Properties Experiments on the Mars Exploration Rovers, Spirit and Opportunity. Measurement Protocols for In Situ Analysis of Organic Compounds at Mars and Comets. Piping Structures on Earth and Possibly Mars: Astrobiological Implications. Uranium and Lead in the Early Planetary Core Formation: New Insights Given by High Pressure and Temperature Experiments. The Mast Cameras and Mars Descent Imager (MARDI) for the 2009 Mars Science Laboratory. MGS MOC: First Views of Mars at Sub-Meter Resolution from Orbit. Analysis of Candor Chasma Interior Layered Deposits from OMEGA/MEX Spectra. Analysis of Valley Networks on Valles Marineris Plateau Using HRSC/MEX Data. Solar Abundance of Elements from Neutron-Capture Cross Sections. Preliminary Evaluation of the Secondary Ion/Accelerator Mass Spectrometer, MegaSIMS. Equilibrium Landforms in the Dry Valleys of Antarctica: Implications for Landscape Evolution and Climate Change on Mars. Continued Study of Ba Isotopic Compositions of Presolar Silicon Carbide Grains from Supernovae. Paleoenviromental Evolution of the Holden-Uzboi Area. Stability of Magnesium Sulfate Minerals in Martian Environments. Tungsten Isotopic Constraints on the Formation and Evolution of Iron Meteorite Parent Bodies. Migration of Dust Particles and Volatiles Delivery to the Inner Planets. On the Sitting of Trapped Noble Gases in Insoluble Organic Matter of Primitive Meteorites. Trapping of Xenon Upon Evaporation-Condensation of Organic Matter Under UV Irradiation: Isotopic Fractionation and Electron Paramagnetic Resonance Analysis. Stability of Water on Mars. A Didactic Activity. Analysis of Coronae in the Parga Chasma Region, Venus. Photometric and Compositional Surface Properties of the Gusev Crater Region, Mars, as Derived from Multi-Angle, Multi-Spectral Investigation of Mars Express HRSC Data. Mapping Compositional Diversity on Mars: Spatial Distribution and Geological Implications. A New Simulation Chamber for Studying Planetary Environments. Folded Structure in Terra Sirenum. Mars. Nitrogen-Noble Gas Static Mass Spectrometry of Genesis Collector Materials. Neon Isotope Heterogeneity in the Terrestrial Mantle: Implication for the Acquisition of Volatile Elements in Terrestrial Planets. The Cosmic Clock, the Cycle of Terrestrial Mass Extinctions.

Source record↗
NASA NTRS2004

Water-Based Pressure Sensitive Paint

Preparation and performance of a water-based pressure sensitive paint (PSP) is described. A water emulsion of an oxygen permeable polymer and a platinum porphyrin type luminescent compound were dispersed in a water matrix to produce a PSP that performs well without the use of volatile, toxic solvents. The primary advantages of this PSP are reduced contamination of wind tunnels in which it is used, lower health risk to its users, and easier cleanup and disposal. This also represents a cost reduction by eliminating the need for elaborate ventilation and user protection during application. The water-based PSP described has all the characteristics associated with water-based paints (low toxicity, very low volatile organic chemicals, and easy water cleanup) but also has high performance as a global pressure sensor for PSP measurements in wind tunnels. The use of a water-based PSP virtually eliminates the toxic fumes associated with the application of PSPs to a model in wind tunnels.

Oglesby, Donald M.↗
NASA NTRS2011

Comparison of Four Strong Acids on the Precipitation Potential of Gypsum in Brines During Distillation of Pretreated, Augmented Urine

Two batches of nominally pretreated and augmented urine were prepared with the baseline pretreatment formulation of sulfuric acid and chromium trioxide. The urine was augmented with inorganic salts and organic compounds in order to simulate a urinary ionic concentrations representing the upper 95 percentile on orbit. Three strong mineral acids: phosphoric, hydrochloric, and nitric acid, were substituted for the sulfuric acid for comparison to the baseline sulfuric acid pretreatment formulation. Three concentrations of oxidizer in the pretreatment formulation were also tested. Pretreated urine was distilled to 85% water recovery to determine the effect of each acid and its conjugate base on the precipitation of minerals during distillation. The brines were analyzed for calcium and sulfate ion, total, volatile, and fixed suspended solids. Test results verified that substitution of phosphoric, hydrochloric, or nitric acids for sulfuric acid would prevent the precipitation of gypsum up to 85% recovery from pretreated urine representing the upper 95 percentile calcium concentration on orbit.

Muirhead, Dean↗
NASA NTRS1995

Chemical Evolution of Interstellar Dust into Planetary Materials

Comets are believed to retain some interstellar materials, stored in fairly pristine conditions since-their formation. The composition and properties of cometary dust grains should reflect those of grains in the outer part of the protosolar nebula which, at least in part, were inherited from the presolar molecular cloud. However, infrared emission features in comets differ from their interstellar counterparts. These differences imply processing of interstellar material on its way to incorporation in comets, but C and N appear to be retained. Overall dust evolution from the interstellar medium (ISM) to planetary materials is accompanied by an increase in proportion of complex organics and a decrease in pure carbon phases. The composition of cometary dust grains was measured in situ during fly-by missions to comet Halley in 1986. The mass spectra of about 5000 cometary dust grains with masses of 5 x 10(exp -17) - 5 x 10(exp -12) g provide data about the presence and relative abundances of the major elements H, C, N, O,Na, Mg, Al, Si, S, Cl, K, Ca, Ti, Cr, Fe, Ni. The bulk abundances of major rock-forming elements integrated over all spectra were found to be solar within a factor of 2, while the volatile elements H, C, N, O in dust are depleted in respect to their total cosmic abundances. The abundances of C and N in comet dust are much closer to interstellar than to meteoritic and are higher than those of dust in the diffuse ISM. In dense molecular clouds dust grains are covered by icy mantles, the average composition of which is estimated to be H:C:N:O = 96:14:1:34. Up to 40% of elemental C and O may be sequestered in mantles. If we use this upper limit to add H, C, N and O as icy mantle material to the abundances residing in dust in the diffuse ISM, then the resulting values for H. C, and N match cometary abundances. Thus, ice mantles undergoing chemical evolution on grains in the dense ISM appear to have been transformed into less volatile and more complex organic residues wherein the H, C and N are largely retained and ultimately accreted in cometary dust. The abundance of O is about the same for cometary dust, meteorites and interstellar dust. In all these samples, most of O in a solid phase is bonded to silicates. In dense molecular clouds, the abundance of O in dust+mantles is significantly higher then in cometary dust. This difference may reflect the greater lability of oxygenated species toward astrophysical processing. Laboratory studies show that O-bearing functional groups in organic compounds tend to be relatively easily removed by heating and/or UV and particle irradiation . In Halley's coma, O-containing organic grains, being unstable, were located closest to the nucleus. The decomposition of the organic grain component in the coma provided a significant extended source contribution to O-containing gaseous species such as CO and H2CO.

Fomenkova, M. N.↗
NASA NTRS1994

Hycrest crested wheatgrass accelerates the degradation of pentachlorophenol in soil

We investigated the effects of vegetation on the fate of pentachlorophenol (PCP) in soil using a novel high-flow sealed test system. Pentachlorophenol has been widely used as a wood preservative, and this highly toxic biocide contaminates soil and ground water at many sites. Although plants are known to accelerate the rates of degradation of certain soil contaminants, this approach has not been thoroughly investigated for PCP. The fate of [14C]PCP, added to soil at a concentration of 100 mg/kg, was compared in three unplanted and three planted systems. The plant used was Hycrest, a perennial, drought-tolerant cultivar of crested wheatgrass [Agropyron desertorum (Fischer ex Link) Schultes]. The flow-through test system allowed us to maintain a budget for 14C-label as well as monitor mineralization (breakdown to 14CO2) and volatilization of the test compound in a 155-d trial. In the unplanted systems, an average of 88% of the total radiolabel remained in the soil and leachate and only 6% was mineralized. In the planted system, 33% of the radiolabel remained in the soil plus leachate, 22% was mineralized, and 36% was associated with plant tissue (21% with the root fraction and 15% with shoots). Mineralization rates were 23.1 mg PCP mineralized kg-1 soil in 20 wk in the planted system, and for the unplanted system 6.6 mg PCP kg-1 soil for the same time period. Similar amounts of volatile organic material were generated in the two systems (1.5%). Results indicated that establishing crested wheatgrass on PCP-contaminated surface soils may accelerate the removal of the contaminant.

Non-NASA Center↗
NASA NTRS2004

Titan Ice and Dust Experiment (TIDE): Detection and Analysis of Compounds of Interest to Astrobiology in the Lower Atmosphere and Surface of Titan

The Titan Orbiter Aerorover Mission (TOAM) is a proposed concept for the Solar System Exploration Visions Mission, Titan Explorer, a follow-on to the Cassini-Huygens mission. TOAM would use a Titan polar orbiter and a lighter-than-air aerorover to investigate the surface and atmosphere of Titan. Astrobiology issues will be addressed though TOAM investigations including, for example: Distribution and composition of organics (atmospheric, aerosol, surface); Organic chemical processes, their chemical context and energy sources; and Seasonal variations and interactions of the atmosphere and surface. The TIDE instrument will perform in-situ analyses to obtain comprehensive and sensitive molecular and elemental assays of volatile organics in the atmosphere, oceans and surface. TIDE chemical analyses are conducted by a Gas Chromatograph-Ion Mobility Spectrometer (GC-IMS). This TIDE GC-IMS was a component of the mini-Cometary Ice and Dust Experiment (mini-CIDEX) developed for the chemical analysis of a cometary environment. Both the GC and helium IMS of mini-CIDEX have been further developed to better meet the analytical and operational requirements of the TOAM. application. A Micro-ElectroMechanical System (MEMS) GC and Mini-Cell helium IMS are under development to replace their respective mini-CIDEX components, providing similar or advanced analytical capabilities.

Kojiro, Daniel R.↗
NASA NTRS2006

Comets, Asteroids, and the Origin of the Biosphere

During the past few decades, the role of comets in the delivery of water, organics, and prebiotic chemicals to the Biosphere of Earth during the Hadean (4.5-3.8 Ga) period of heavy bombardment has become more widely accepted. However comets are still largely regarded as frigid, pristine bodies of protosolar nebula material that are entirely devoid of liquid water and consequently unsuitable for life in any form. Complex organic compounds have been observed comets and on the water rich asteroid 1998 KY26, which has color and radar reflectivity similar to the carbonaceous meteorites. Near infrared observations have indicated the presence of crystalline water ice and ammonia hydrate on the large Kuiper Belt object (50000) Quaoar with resurfacing that may indicate cryovolcanic outgassing and the Cassini spacecraft has detected water-ice geysers on Saturn s moon Enceladus. Spacecraft observations of the chemical compositions and characteristics of the nuclei of several comets (Halley, Borrelly, Wild 2, and Tempel 1) have now firmly established that comets contain a suite of complex organic chemicals; water is the predominant volatile; and that extremely high temperatures (approx.350-400 K) can be reached on the surface of the very black (albedo-0.03) nuclei when the comets are with 1.5 AU from the Sun. Impact craters and pinnacles observed on comet Wild 2 suggest a thick crust and episodic outbursts and jets observed on the nuclei of several comets are interpreted as indications that localized regimes of liquid water and water vapor can periodically exist beneath the crust of some comets. The Deep Impact observations indicate that the temperature on the nucleus of of comet Tempel 1 at 1.5 AU varied from 330K on the sunlit side to a minimum of 280+/-8 K. It is interesting that even the coldest region of the comet surface was slightly above the ice/liquid water phase transition temperature. These results suggest that pools and films of liquid water can exist in a wide range of temperatures in cavities and voids at different depths just beneath the crust of a comet. The possibility that liquid water may exist over a wide range of temperatures on comets significantly enhances the possibility that these bodies may harbor niches suitable for microbial communities and ecosystems. Such niches would by ideal for the growth of psychrophilic, mesophilic, and possibly even thermophilic chemolithotrophs and photoautotrophs such as the motile filamentous cyanobacteria (e.g., Calothrix, Oscillatoria, Phormidium, and Spirulina) that can grow in geothermal springs and geysers at temperatures ranging from 320K to 345K and in cold polar desert soils. This paper reviews the observational data in support of the hypothesis that liquid water can exist in permafrost-like active regions just beneath the surface of comets when near perihelion and provides additional arguments in support of the hypothesis that comets, carbonaceous meteorites, and asteroids may have played a significant role in the origin and evolution of the Biosphere and in the distribution of microbial life throughout the Solar System.

Hoover, Richard B.↗
NASA NTRS2000

Photochemistry Saturn's Atmosphere: Effects of an Influx of External Oxygen - 2

We use a one-dimensional diurnally averaged model of photochemistry and diffusion in Saturn's stratosphere to investigate the influence of extraplanetary debris on atmospheric chemistry. In particular, we consider the effects of an influx of oxygen from micrometeoroid ablation or from ring-particle diffusion; the contribution from cometary impacts, satellite debris, or ring vapor is deemed to be less important. The photochemical model results are compared directly with Infrared Space Observatory (ISO) observations to constrain the influx of extraplanetary oxygen to Saturn. From the ISO observations, we determine that the column densities of CO2 and H2O above 10 mbar in Saturn's atmosphere are (6.3 +/- 1) x 10(exp 14) and (1.4 +/- 0.4) x 10(exp 15)/ square cm, respectively; our models indicate that a globally averaged oxygen influx of (4+/-2) x 10(exp 6) O atoms /sq cm/s is required to explain these observations. Models with a locally enhanced influx of H20 operating over a small fraction of the projected area do not provide as good a fit to the ISO H2O observations. If volatile oxygen compounds comprise one-third to one-half of the exogenic source by mass, then Saturn is currently being bombarded with (3 +/- 2) x 10(exp -16) g/square cm/s of extraplanetary material. To reproduce the observed CO2/H2O ratio in Saturn's stratosphere, some of the exogenic oxygen must arrive in the form of a carbon-oxygen bonded species such as CO or CO2. An influx consistent with the composition of cometary ices fails to reproduce the high observed CO2/H2O ratio, suggesting that (i) the material has ices that are slightly more carbon-rich than is typical for comets, (ii) a contribution from an organic-rich component is required, or (iii) some of the hydrogen-oxygen bonded material is converted to carbon-oxygen bonded material without photochemistry (e.g., during the ablation process). We have also reanalyzed the 5-micron CO observations of Noll and Larson and determine that the CO lines are most sensitive to the 100- to 400-mbar column density for which we derive a range of (0.7-1.5) x 10(exp 17)/square cm; the CO observations do not allow us to distinguish between an external or internal source of CO on Saturn. If we assume that all the extraplanetary oxygen derives from a micrometeoroid source, then the unfocused dust flux at 9.5 AU must be (i) (1 +/- 0.7) x 10(exp -16) g/square cm/s if interstellar grains are the source of the external oxygen on Saturn, (ii) (4 +/- 3) x 10 (exp -17) g/ sq. cm./s if IDPs on randomly inclined, highly eccentric orbits (e.g., Halley-type comet grains) are the source of the external oxygen, or (iii) (2+/- 1.4) x 10(exp -18)/g/sq cm/s if IDPs on low inclination, low eccentricity orbits (e.g., Kuiper-belt grains) are the source of the external oxygen. These estimates can be used in combination with future Cassini dust detection data to determine the ultimate source of the dust at Saturn's distance from the Sun.

Moses, Julianne I.↗
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 NTRS2005

In situ Analysis of Organic Compounds on Mars using Chemical Derivatization and Gas Chromatography Mass Spectrometry

One of the core science objectives of NASA's 2009 Mars Science Laboratory (MSL) mission is to determine the past or present habitability of Mars. The search for key organic compounds relevant to terrestrial life will be an important part of that assessment. We have developed a protocol for the analysis of amino acids and carboxylic acids in Mars analogue materials using gas chromatography mass spectrometry (GCMS). As shown, a variety of carboxylic acids were readily identified in soil collected from the Atacama Desert in Chile at part-per-billion levels by GCMS after extraction and chemical derivatization using the reagent N,N-tert.-butyl (dimethylsilyl) trifluoroacetamide (MTBSTFA). Several derivatized amino acids including glycine and alanine were also detected by GCMS in the Atacama soil at lower concentrations (chromatogram not shown). Lacking derivatization capability, the Viking pyrolysis GCMS instruments could not have detected amino acids and carboxylic acids, since these non-volatile compounds require chemical transformation into volatile species that are stable in a GC column. We are currently optimizing the chemical extraction and derivatization technique for in situ GCMS analysis on Mars. Laboratory results of analyses of Atacama Desert samples and other Mars analogue materials using this protocol will be presented.

Glavin, D. P.↗