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Initial results indicate that ionic liquids are promising media for the extraction of oxygen from lunar regolith. IL acid systems can solubilize regolith and produce water with high efficiency. IL electrolytes are effective for water electrolysis, and the spent IL acid media are capable of regeneration.
The Europan Molecular Indicators of Life Investigation (EMILI) is an instrument concept being developed for the Europa Lander mission currently under study. EMILI will meet and exceed the scientific and technical/resource requirements of the organic composition analyzer identified as a core instrument on the Lander. EMILI tightly couples two complementary analytical techniques, based on 1) liquid extraction and processing with capillary electrophoresis and 2) thermal and chemical extraction with gas chromatography, to robustly detect, structurally characterize, and quantify the broadest range of organics and other Europan chemicals over widely-varying concentrations. Dual processing and analysis paths enable EMILI to perform a thorough characterization of potential molecular biosignatures and contextual compounds in collected surface samples. Here we present a summary of the requirements, design, and development status of EMILI with projected scientific opportunities on the Europa Lander as well as on other potential life detection missions seeking potential molecular biosignatures in situ.
An extraction device is disclosed comprising a tube containing a substantially inert, chemically non-reactive packing material with a large surface area to volume ratio. A sample which consists of organic compounds dissolved in a liquid, is introduced into the tube. As the sample passes through the packing material it spreads over the material's large surface area to form a thin liquid film which is held on the packing material in a stationary state. A particular group or family of compounds is extractable from the sample by passing a particular solvent system consisting of a solvent and selected reagents through the packing material. The reagents cause optimum conditions to exist for the compounds of the particular family to pass through the phase boundary between the sample liquid and the solvent of the solvent system. Thus, the compounds of the particular family are separated from the sample liquid and become dissolved in the solvent of the solvent system. The particular family of compounds dissolved in the solvent, representing an extract, exits the tube together with the solvent through the tube's nozzle, while the rest of the sample remains on the packing material in a stationary state. Subsequently, a different solvent system may be passed through the packing material to extract another family of compounds from the remaining sample on the packing material.
Liquid carbon dioxide inexpensive solvent. Inexpensive process proposed for removing such poisons as furfural and related compounds from fermentation baths of biomass hydrolysates. New process based on use of liquid carbon dioxide as extraction solvent. Liquid CO2 preferable to such other liquid solvents as ether or methylene chloride.
A sample processor and method for the automatic extraction of families of compounds, known as extracts, from liquid and/or homogenized solid samples are disclosed. The sample processor includes a tube support structure which supports a plurality of extraction tubes, each containing a sample from which families of compounds are to be extracted. The support structure is moveable automatically with respect to one or more extraction stations, so that as each tube is at each station a solvent system, consisting of a solvent and reagents, is introduced therein. As a result an extract is automatically extracted from the tube. The sample processor includes an arrangement for directing the different extracts from each tube to different containers, or to direct similar extracts from different tubes to the same utilization device.
The Molecular Analyzer for Complex Refractory Organic-rich Surfaces, MACROS, is a novel instrument package being developed at NASA Goddard Space Flight Center. MACROS enables the in situ characterization of a sample's composition by coupling two powerful techniques into one compact instrument package: (1) laser desorption/ionization time-of-flight mass spectrometry (LDMS) for broad detection of inorganic mineral composition and non-volatile organics, and (2) liquid-phase extraction methods to gently isolate the soluble organic and inorganic fraction of a planetary powder for enrichment and detailed analysis by liquid chromatographic separation coupled to LDMS. The LDMS is capable of positive and negative ion detection, precision mass selection, and fragment analysis. Two modes are included for LDMS: single laser LDMS as the broad survey mode and two step laser mass spectrometry (L2MS). The liquid-phase extraction will be done in a newly designed extraction module (EM) prototype, providing selectivity in the analysis of a complex sample. For the sample collection, a diamond drill front end will be used to collect rock/icy powder. With all these components and capabilities together, MACROS offers a versatile analytical instrument for a mission targeting an icy moon, carbonaceous asteroid, or comet, to fully characterize the surface composition and advance our understanding of the chemical inventory present on that body.
The design criteria for heterogeneous chemical reactions in liquid/liquid systems formally correspond to those of classical physical extraction. More complex models are presented which describe the material exchange at the individual droplets in an extraction with chemical reaction and in liquid membrane permeation.
The continued search for organics on Mars will require the development of simplified procedures for handling and processing of soil or rock core samples prior to analysis by onboard instrumentation. Extraction of certain organic molecules such as amino acids from rock and soil samples using a liquid solvent (H2O) has been shown to be more efficient (by approximately an order of magnitude) than heat extraction methods. As such, liquid extraction (using H2O) of amino acid molecules from rock cores or regolith material is a prime candidate for the required processing. In this scenario, electrospray ionization (ESI) of the liquid extract would be a natural choice for ionization of the analyte prior to interrogation by one of a variety of potential analytical separation techniques (mass spectroscopy, ion mobility spectroscopy, etc.). Aside from the obvious compatibility of ESI and liquid samples, ESI offers simplicity and a soft ionization capability. In order to demonstrate that liquid extraction and ESI can work as part of an in situ instrument on Mars, we must better understand and quantify the effect salts have on the ESI process. In the current work, we have endeavored to investigate the feasibility and limitations of negative mode ESI of Martian surface samples in the context of sample salt content using ion mobility spectroscopy (IMS).
The use of Biofuels has been gaining in popularity over the past few years due to their ability to reduce the dependence on fossil fuels. Biofuels as a renewable energy source can be a viable option for sustaining long-term energy needs if they are managed efficiently. We describe our initial efforts to exploit algae, halophytes and other non-crop plants to produce synthetics for fuel blends that can potentially be used as fuels for aviation and non-aerospace applications. Our efforts have been dedicated to crafting efficient extraction and refining processes in order to extract constituents from the plant materials with the ultimate goal of determining the feasibility of producing biomass-based jet fuel from the refined extract. Two extraction methods have been developed based on communition processes, and liquid-solid extraction techniques. Refining procedures such as chlorophyll removal and transesterification of triglycerides have been performed. Gas chromatography in tandem with mass spectroscopy is currently being utilized in order to qualitatively determine the individual components of the refined extract. We also briefly discuss and compare alternative methods to extract fuel-blending agents from alternative biofuels sources.
An important concern with long-duration manned space travel is the need to furnish enough materials to the vehicle, as well as the crew, for the duration of the mission. By extracting oxygen from the oxides present in regolith, propellant and life support could be supplied to the vehicle and the crew while in space, thereby limiting the amount of supplies needed prior to lift-off. Using a class of compounds known as ionic liquids, we have been able to lower the electrolysis operating temperature from 1600 C (molten oxide electrolysis) to less than 200 C, making this process much more feasible in terms of energy consumption and materials handling. To make this process ready for deployment into space, we have investigated what steps of the process would be affected by the low-gravity environment in space. In the lab, the solubilization of lunar regolith simulant in ionic liquid produces water vapor that is normally distilled out of solution and subsequently electrolyzed for oxygen production. This distillation is not possible in space, so we have tested a method known as pervaporation and have suggested a way this technique could be incorporated into a reactor design.
A basic requirement of large scale solar cell fabrication is to provide low cost base material. Unconventional refining of metallurical grade silicon represents one of the most promising ways of silicon meltstock processing. The refining concept is based on an optimized combination of metallurgical treatments. Commercially available crude silicon, in this sequence, requires a first pyrometallurgical step by slagging, or, alternatively, solvent extraction by aluminum. After grinding and leaching, high purity qualtiy is gained as an advanced stage of refinement. To reach solar grade quality a final pyrometallurgical step is needed: liquid-gas extraction.
The topics include: 1) The abundances of Iron-60 in Pyroxene Chondrules from Unequilibrated Ordinary Chondrites; 2) LL-Ordinary Chondrite Impact on the Moon: Results from the 3.9 Ga Impact Melt at the Landing Site of Appolo 17; 3) Evaluation of Chemical Methods for Projectile Identification in Terrestrial and Lunar Impactites; 4) Impact Cratering Experiments in Microgravity Environment; 5) New Achondrites with High-Calcium Pyroxene and Its implication for Igneous Differentiation of Asteroids; 6) Climate History of the Polar Regions of Mars Deduced form Geologic Mapping Results; 7) The crater Production Function for Mars: A-2 Cumulative Power-Law Slope for Pristine Craters Greater than 5 km in Diameter Based on Crater Distribution for Northern Plains Materials; 8) High Resolution Al-26 Chronology: Resolved Time Interval Between Rim and Interior of a Highly Fractionated Compact Type a CAI from Efremovka; 9) Assessing Aqueous Alteration on Mars Using Global Distributions of K and Th; 10) FeNi Metal Grains in LaPaz Mare Basalt Meteorites and Appolo 12 Basalts; 11) Unique Properties of Lunar Soil for In Situ Resource Utilization on the Moon; 12) U-Pb Systematics of Phosphates in Nakhlites; 13) Measurements of Sound Speed in Granular Materials Simulated Regolith; 14) The Effects of Oxygen, Sulphur and Silicon on the Dihedral Angles Between Fe-rich Liquid Metal and Olivine, Ringwoodite and Silicate Perovskite: Implications for Planetary Core Formation; 15) Seismic Shaking Removal of Craters 0.2-0.5 km in Diameter on Asteroid 433 Eros; 16) Focused Ion Beam Microscoopy of ALH84001 Carbonate Disks; 17) Simulating Micro-Gravity in the Laboratory; 18) Mars Atmospheric Sample Return Instrument Development; 19) Combined Remote LIBS and Raman Spectroscopy Measurements; 20) Unusual Radar Backscatter Properties Along the Northern Rim of Imbrium Basin; 21) The Mars Express/NASAS Project at JPL; 22) The Geology of the Viking 2 Lander Site Revisited; 23) An Impact Genesis for Loki Patera? 24) Mars Polar Cap Edges Tracked over 3 Full Mars Years; 25) Elemental Abundance in Presolar SiC: Comparing Grains Separated by Acid Residue and Gently Separation Procedures; 26) First Results from the Descent Imager/Spectral Radiometer (DISR) Experiment on the Huygens Entry Probe of Titan; 27) Minor Element Behavior of Pallasite Olivine: Understanding Pallasite Thermal History and Chronology; 28) Canonical Anorthite in a Grosnaja Forsterite-bearing CAI; 29) Experimental Evidence for Condensation of 'Astrophysical' Carbonate; 30) Distribution and Classification of Multiple Coronae on Venus; 31) Recognition of Rayed Craters on Mars in THEMIS Thermal Infrared Imagery: Implications for Martian Meteorite Source Regions; 32) Geochemical Modeling of Evaporites on Mars: Insight from Meridiani Planum; 33) Hadean Crustal Processes Revealed from Oxygen Isotopes and U-Th-Pb Depth Profiling of Pre-4.0 Ga Detrital Zircons from Western Australia; 34) On Modeling the Seepage of Water into the Martian Subsurface; 35) Martial Gullies and Groundwater: A Series of Unfortunate Exceptions; 36) Olivine and Carbonate Globules in ALH84001: A Terrestrial Analog, and Implications for Water on Mars; 37) A Reevaluation of Mass Movements Within the Valles Marineris Region of Mars Using MOLA and MOC Data; 38) Evidence of Hydrated 109P/Swift-Tuttle Meteoroids from Meteor Spectroscopy; 39) Cr-54 Anomalies in the Solar System: Their Extent and Origin; 40) Reevaluation of the Mn-53-Cr-53 Systematic in the Basaltic Achondrites; 41) Effective Liquid Metal-Silicate Mixing Upon Shock by Power-Law Droplet Size Scaling in Richtmyer-Meshkov Like Perturbations; 42) Post-Impact Deformation of Impact Craters: Towards a Better Understanding Through the Study of Mjolnir Crater; 43) Cutting Silica Aerogel for Particle Extraction; 44) Liquid Hydrocarbons on Titan's Surface? How Cassini ISS Observations Fit into the Story (So Far); and 45) Mesoscale Simulations of Polar Circulations: Late Spring to Late Summe
In the robotic search for life on Mars, different proposed missions will analyze the chemical and biological signatures of life using different platforms. The analysis of samples via analytical instrumentation on the surface of Mars has thus far only been attempted by the two Viking missions. Robotic arms scooped relogith material into a pyrolysis oven attached to a GC/MS. No trace of organic material was found on any of the two different samples at either of the two different landing sites. This null result puts an upper limit on the amount of organics that might be present in Martian soil/rocks, although the level of detection for each individual molecular species is still debated. Determining the absolute limit of detection for each analytical instrument is essential so that null results can be understood. This includes investigating the trade off of using pyrolysis versus liquid solvent extraction to release organic materials (in terms of extraction efficiencies and the complexity of the sample extraction process.) Extraction of organics from field samples can be accomplished by a variety of methods such utilizing various solvents including HCl, pure water, supercritical fluid and Soxhelt extraction. Utilizing 6N HCl is one of the most commonly used method and frequently utilized for extraction of organics from meteorites but it is probably infeasible for robotic exploration due to difficulty of storage and transport. Extraction utilizing H2O is promising, but it could be less efficient than 6N HCl. Both supercritical fluid and Soxhelt extraction methods require bulky hardware and require complex steps, inappropriate for inclusion on rover spacecraft. This investigation reports the efficiencies of pyrolysis and solvent extraction methods for amino acids for different terrestrial samples. The samples studied here, initially created in aqueous environments, are sedimentary in nature. These particular samples were chosen because they possibly represent one of the best terrestrial analogs of Mars and they represent one of the absolute best case scenarios for finding organic molecules on the Martian surface.
Polyimide aerogels are a nanoporous material made by extracting the liquid portion of a wet gel and replacing it with air, while still maintaining the porous solid internal architecture. This results in a material with extremely low densities, low thermal conductivities, high internal surfaces areas, and low dielectric constants. Currently, complex aerogel forms are not possible, since they require molds in order to be shaped. To overcome this challenge, we are attempting to use various additive manufacturing techniques to produce complex architectures. Three different approaches are being studied to accomplish this. One is to print using a viscous wet gel and have the structure solidify at the end of the print, another is to use a mixing tip, where a less viscous gel and the final chemical that causes gelation will be mixed as it is printing, allowing it to gel layer by layer, and the third is to use a UV curable aerogel with a UV light following behind to solidify the gel as it prints. To have these approaches be successful, the printing parameters and the aerogel's chemical formulation need to be optimized. The more harmonious these two factors can be made, the more defined and complex the resulting structure can be. Preliminary results show that 3D printing polyimide aerogels are a viable option, but further optimization must occur for reliable printing.
Future missions to Enceladus, Europa, Mars, and beyond may seek the molecular signs of extraterrestrial life through chemical analysis of acquired samples. Particularly on ocean worlds such as Enceladus and Europa, samples may contain trace ocean-borne molecular biosignatures of extant life that may or may not share similarities to those of terrestrial life. In situ analyses must be prepared to detect and characterize a wide range of possible molecular species, structures, and patterns, typically with exquisite sensitivity and within a complex, poorly-characterized planetary environment. The Extraterrestrial Molecular Indicators of Life Investigation (EMILI) is designed to meet or exceed the requirements of such missions for organic molecular analysis through a powerful combination of dual chemical separation and both optical and mass spectrometry detection techniques, realized in an integrated, compact instrument package fully compatible with anticipated flight resources and conditions. The full EMILI instrument combines two sample analysis subsystems to provide wide-ranging and complementary detection of organic compounds and inorganic salts. The Gas Analysis Processing System (GAPS) uses a chemical derivatization protocol with gas chromatography (GC) separation prior to detection in an ion trap mass spectrometer (ITMS) to enable full characterization of lower-polarity, volatile and semi-volatile molecules such as fatty acids and hydrocarbons. The Organic Capillary Electrophoresis ANalysis System (OCEANS) uses a liquid-based extraction protocol with CE separation to enable precise analysis of more water-soluble/polar compounds. OCEANS features a laser-induced fluorescence detection mode to perform ultra-sensitive quantitative analysis of chiral amino acids. In EMILI, OCEANS is additionally coupled to the same ITMS through a novel electrospray ionization interface. The common ITMS allows EMILI to identify and cross-correlate molecular species and patterns, detected through either or both protocols, of molecular weights to over 1000 u, potentially even revealing complex biosignatures such as alien oligopeptides and informational polymers.
Description of one approach to the analysis for carbon compounds in lunar materials from the Apollo 11 mission. The sequential scheme followed generally accepted organic geochemical practices, but was unusual in its application to a single sample. The procedures of the scheme were designed to minimize handling of the solids and extracts or hydrolysates. The solid lunar sample was retained in all steps of the sequential analysis in the vessel in which it was originally placed. Centrifugation was used to separate solid and liquid phases after extraction or refluxing. Liquids were recovered from solids by decantation.
Four subjects completed five treadmill training sessions under comfortable to cool conditions and were calibrated to find an optimum combination of speed and grade on the treadmill which would produce a metabolic rate of 2000 Btu-hr. Dressed in an Apollo liquid cooling garment, each man underwent a total of four experiments in which the rate of heat extraction from the liquid cooling garment was adjusted to an amount which would cause a storage within the body of 1000 Btu/hr. Physiological measurements included skin temperature at 9 locations, rectal and ear canal probes, and heart rate. The increases in tolerance time for the various subjects and the various methods of emergency cooling, ranged from a low of six minutes to a high of 48 minutes, or from 8 to 102% of the baseline tolerance times. The largest gains were achieved in a subject whose tolerance endpoint was atypical, and whose baseline heat tolerance was unsually low.