Engineering topics
Publications and source records attributed to Mahaffy, P. R..
The Cometary Atmosphere Simulator (CASIM) is designed to simulate in 2-D and 3-D the complex interaction between the cometary atmosphere and the hypersonic solar wind using a multi-fluid approach. Our simulator is based on the solution of multi-fluid equations using an efficient adaptive Cartesian mesh. It is designed to use the capabilities of highly parallel super-cluster computers.
The determination of the abundance and chemical and isotopic composition of organic molecules in comets and those that might be found in protected environments at Mars is a first step toward understanding prebiotic chemistries on these solar system bodies. While future sample return missions from Mars and comets will enable detailed chemical and isotopic analysis with a wide range of analytical techniques, precursor insitu investigations can complement these missions and facilitate the identification of optimal sites for sample return. Robust automated experiments that make efficient use of limited spacecraft power, mass, and data volume resources are required for use by insitu missions. Within these constraints we continue to explore a range of instrument techniques and measurement protocols that can maximize the return from such insitu investigations.
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.
The Odyssey Missions orbital maps of near surface ice abundance using neutron spectroscopy (Boynton et al., 2002), the Mars Exploration Rover s confirmation of aqueous processing (Squyres et al., 2004), and the Mars Express detailed infrared maps of specific mineral types that were likely formed in aqueous environments (Bibring et al., 2005) have dramatically expanded our tool set for understanding of aqueous processes on Mars. The 2009 Mars Science Laboratory is designed to extend the "follow the water" crosscutting theme of the Mars Exploration Program toward an even more detailed exploration of habitability - the potential of the Mars environment to support life. The next steps in understanding the habitability of Mars are a more detailed in situ analysis of the chemical state of elements such as C, H, O, N, S, P, Ca, and Fe that are essential for terrestrial life. Of particular interest are experiments that establish definitive mineralogy for a wider range of compounds and those that implement a more comprehensive and sensitive search for organic molecules both in the atmosphere and in surface or near surface rocks, soils, and fines. The recent reports of atmospheric methane in the Martian atmosphere make the organics exploration even more compelling. The substantial mass and power resources of MSL combined with its mobility and powerful sample acquisition and processing tools will enable it to locate a variety of near-surface samples and analyze these in some detail. NASA is presently considering the possibility of landing a second MSL rover in 2011.
The detailed characterization of organic compounds that might be preserved in rocks, ices, or sedimentary layers on Mars would be a significant step toward resolving the question of the habitability and potential for life on that planet. The fact that the Viking gas chromatograph mass spectrometer (GCMS) did not detect organic compounds should not discourage further investigations since (a) an oxidizing environment in the near surface fines analyzed by Viking is likely to have destroyed many reduced carbon species; (b) there are classes of refractory or partially oxidized species such as carboxylic acids that would not have been detected by the Viking GCMS; and (c) the Viking landing sites are not representative of Mars overall. These factors motivate the development of advanced in situ analytical protocols to carry out a comprehensive survey of organic compounds in martian regolith, ices, and rocks. We combine pyrolysis GCMS for analysis of volatile species, chemical derivatization for transformation of less volatile organics, and laser desorption mass spectrometry (LDMS) for analysis of elements and more refractory, higher-mass organics. To evaluate this approach and enable a comparison with other measurement techniques we analyze organics in Mars simulant samples.
The exploration of the possible emergence and duration of life on Mars from landed platforms requires attention to the quality of measurements that address these objectives. In particular, the potential impact of terrestrial contamination on the measurement of reduced carbon with sensitive in situ instruments must be addressed in order to reach definitive conclusions regarding the source of organic molecules. Following the recommendation of the Mars Exploration Program Analysis Group (MEPAG) at its September 2003 meeting [MEPAG, 2003], the Mars Program Office at NASA Headquarters chartered the Organic Contamination Science Steering Group (OCSSG) to address this issue. The full report of the six week study of the OCSSG can be found on the MEPAG web site [1]. The study was intended to define the contamination problem and to begin to suggest solutions that could provide direction to the engineering teams that design and produce the Mars landed systems. Requirements set by the Planetary Protection Policy in effect for any specific mission do not directly address this question of the potential interference from terrestrial contaminants during in situ measurements.
One of the primary objectives of the 1976 Viking missions was to determine whether organic compounds, possibly of biological origin, were present in the Martian surface soils. The Viking gas chromatography mass spectrometry (GCMS) instruments found no evidence for any organic compounds of Martian origin above a few parts per billion in the upper 10 cm of surface soil, suggesting the absence of a widely distributed Martian biota. However, it is now known that key organic compounds important to biology, such as amino acids, carboxylic acids and nucleobases, would likely have been missed by the Viking GCMS instruments. In this study, a Mars soil analogue that was inoculated with approx. 10 billion Escherichia coli cells was heated at 500 C under Martian ambient pressure to release volatile organic compounds from the sample. The pyrolysis products were then analyzed for amino acids and nucleobases using high performance liquid chromatography (HPLC) and GCMS. 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 by the Viking GCMS instruments. Upcoming strategies for Mars exploration will require in-situ analyses by instruments that can assess whether any organic compounds, especially those that might be associated with life, are present in Martian surface samples.
One of the primary objectives of the 1976 Viking missions was to determine whether organic compounds, possibly of biological origin, were present in the Martian surface soils. The Viking gas chromatography mass spectrometry (GCMS) instruments found no evidence for any organic compounds of Martian origin above a few parts per billion in the upper 10 cm of surface soil [l], suggesting the absence of a widely distributed Martian biota. However, Benner et d. have suggested that significant amounts of non-volatile organic compounds, possibly including oxidation products of bioorganic molecules (e.g. carboxylic acids) would not have been detected by the Viking GCMS [2]. Moreover, other key organic compounds important to biology, such as amino acids and nucleobases, would also likely have been missed by the Viking GCMS as these compounds require chemical derivatization to be stable in a GC column [3]. Recent pyrolysis experiments with a Mars soil analogue that had been innoculated with Escherichia coli bacteria have shown that amino acid decomposition products (amines) and nucleobases are among the most abundant products generated after pyrolysis of the bacterial cells [4,5]. At the part per billion level (Viking GCMS detection limit), these pyrolysis products generated from several million bacterial cells per gram of Martian soil would not have been detected by the Viking GCMS instruments [4]. Analytical protocols are under development for upcoming in situ lander opportunities to target several important biological compounds including amino acids and nucleobases. For example, extraction and chemical derivatization techniques [3] are being adapted for space flight use to transform reactive or fragile molecules that would not have been detected by the Viking GCMS instruments, into species that are sufficiently volatile to be detected by GCMS. Recent experiments carried out at NASA Goddard have shown that using this derivatization technique all of the targeted compounds mentioned above can be separated on a GC column and detected by MS at sub-picomole (< 10(exp -l2 mole) levels. With these methods, the detection limit for amino acids, carboxylic acids and nucleobases is several orders of magnitude more sensitive than the Viking GCMS instruments for these compounds. Preliminary results using this analytical technique on a variety of Martian soil analogues will be presented.
The next landed missions to Mars, such as the planned Mars Science Laboratory and ExoMars, will require sample analysis capabilities refined well beyond what has been flown to date. A key science objective driving this requirement is the determination of the carbon inventory of Mars, and particularly the detection of organic compounds. While the gas chromatograph mass spectrometers (GCMS) on the Viking landers did not detect any indigenous organics in near surface fines, it is possible that these measurements were not representative of Mars on the whole. That is, those compounds to which the GC/MS was sensitive would likely not have survived the strong oxidative decomposition in the regolith at the landing sites in question. The near surface fines could very well contain a significant quantity of refractory compounds that would not have been volatilized in the sample ovens on Viking. It is also possible that volatile organics exist on Mars in sedimentary, subsurface, or polar niches.
Ground-penetrating radar (GPR) offers the exciting possibility of remote sensing below the Martian surface for trapped aquifers. A GPR is currently heading to Mars onboard Mars Express (MEX) and a GPR is in consideration to be onboard Mars Reconnaissance Orbiter (MRO) in 2005. While such orbital systems offer great potential for polar stratigraphy studies, their ability to penetrate deep into the Martian polar ice is a function of both the intervening ionospheric density and the overlying ground ice conductivity. The influence of both signal-altering layers will be discussed. Polar Ice and Water: Clifford1,2 has suggested
Montgolfiere balloons can provide a unique near-surface platform for an extended traverse over the polar regions of Mars. During the polar summer, such solar powered balloons would remain in the constant sun of the polar summer and could remain airborne for many weeks or even months as the atmospheric circulation would drive the balloons around the polar region many times before the balloon would cross the terminator. Such a platform for scientific measurements could provide in situ sampling of the atmosphere for trace disequilibrium species that might be indicators of present geological or biological activity in this region. It could furthermore provide high resolution imaging, deep electromagnetic (EM) sounding for subsurface stratigraphy and liquid water, and high spatial resolution neutron measurements of subsurface ice. Technologies for robust balloon deployment on entry and controlled encounters with the surface and near subsurface for sample acquisition in otherwise inaccessible regions are presently being studied and developed with support from NASA.
Montgolfiere balloons can provide a unique near-surface platform for an extended traverse over the polar regions of Mars. During the polar summer, such solar powered balloons would remain in the constant sun of the polar summer and could remain airborne for many weeks or even months as the atmospheric circulation would drive the balloons around the polar region many times before the balloon would cross the terminator. Such a platform for scientific measurements could provide in situ sampling of the atmosphere for trace disequilibrium species that might be indicators of present geological or biological activity in this regon. It could furthermore provide high resolution imaging, deep electromagnetic (EM) sounding for subsurface stratigraphy and liquid water, and high spatial resolution neutron measurements of subsurface ice. Technologies for robust balloon deployment on entry and controlled encounters with the surface and near subsurface for sample acquisition in otherwise inaccessible regions are presently being studied and developed with support from NASA.
We present details of a miniature integrated time-of-flight mass spectrometer and sample handling system under development to address some of the needs for in situ sample analysis on landed missions. Additional information is contained in the original extended abstract.
In response to the question 'what to do next' at Mars we explore the value of a high precision in situ measurement of isotopic and trace gas constituents in the atmosphere combined with a similar analysis of gas extracted from near surface rocks and soils. The scientific goals are to advance our understanding of the evolution of the Martian atmosphere and to search for fossils of past geochemical conditions. One element of this program that ties directly to the goals of the Astrobiology Program will be a sensitive search for simple or complex organic molecules contained in the atmosphere and in the solid phase. The broad chemical and isotopic analysis planned insures that a highly successful program will be carried out even if no organics are detected. We will demonstrate that the technology to carry out this Program is presently in hand.
New laboratory studies employing the Engineering Unit (EU) of the Galileo Probe Mass Spectrometer (GPMS) have resulted in a substantial reduction in the previously reported upper limit on the ammonia mixing ratio derived from the GPMS experiment at Jupiter. This measurement is complicated by background ammonia contributions in the GPMS during direct atmospheric sampling produced from the preceding gas enrichment experiments. These backgrounds can be quantified with the data from the EU studies when they are carried out in a manner that duplicates the descent profile of pressure and enrichment cell loading. This background is due to the tendency of ammonia to interact strongly with the walls of the mass spectrometer and on release to contribute to the gas being directly directed into the ion source from the atmosphere through a capillary pressure reduction leak. It is evident from the GPMS and other observations that the mixing ratio of ammonia at Jupiter reaches the deep atmosphere value at substantially higher pressures than previously assumed. This is a likely explanation for the previously perceived discrepancy between ammonia values derived from ground based microwave observations and those obtained from attenuation of the Galileo Probe radio signal.
The Galileo Probe entered the atmosphere of Jupiter on December 7, 1995. Measurements of the chemical and isotopic composition of the Jovian atmosphere were obtained by the mass spectrometer during the descent over the 0.5 to 21 bar pressure region over a time period of approximately 1 hour. The sampling was either of atmospheric gases directly introduced into the ion source of the mass spectrometer through capillary leaks or of gas, which had been chemically processed to enhance the sensitivity of the measurement to trace species or noble gases. The analysis of this data set continues to be refined based on supporting laboratory studies on an engineering unit. The mixing ratios of the major constituents of the atmosphere hydrogen and helium have been determined as well as mixing ratios or upper limits for several less abundant species including: methane, water, ammonia, ethane, ethylene, propane, hydrogen sulfide, neon, argon, krypton, and xenon. Analysis also suggests the presence of trace levels of other 3 and 4 carbon hydrocarbons, or carbon and nitrogen containing species, phosphine, hydrogen chloride, and of benzene. The data set also allows upper limits to be set for many species of interest which were not detected. Isotope ratios were measured for 3He/4He, D/H, 13C/12C, 20Ne/22Ne, 38Ar/36Ar and for isotopes of both Kr and Xe.
The composition of the jovian atmosphere from 0.5 to 21 bars along the descent trajectory was determined by a quadrupole mass spectrometer on the Galileo probe. The mixing ratio of He (helium) to H2 (hydrogen), 0.156, is close to the solar ratio. The abundances of methane, water, argon, neon, and hydrogen sulfide were measured; krypton and xenon were detected. As measured in the jovian atmosphere, the amount of carbon is 2.9 times the solar abundance relative to H2, the amount of sulfur is greater than the solar abundance, and the amount of oxygen is much less than the solar abundance. The neon abundance compared with that of hydrogen is about an order of magnitude less than the solar abundance. Isotopic ratios of carbon and the noble gases are consistent with solar values. The measured ratio of deuterium to hydrogen (D/H) of (5 +/- 2) x 10(-5) indicates that this ratio is greater in solar-system hydrogen than in local interstellar hydrogen, and the 3He/4He ratio of (1.1 +/- 0.2) x 10(-4) provides a new value for protosolar (solar nebula) helium isotopes. Together, the D/H and 3He/4He ratios are consistent with conversion in the sun of protosolar deuterium to present-day 3He.