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Gas chromatography has proven to be a very useful analytical technique for in situ analysis of extraterrestrial environments as demonstrated by its successful operation on spacecraft missions to Mars and Venus. The technique is also one of the six scientific instruments aboard the Huygens probe to explore Titan's atmosphere and surface. A review of gas chromatography in previous space missions and some recent developments in the current environment of fiscal constraints and payload size limitations are presented.

Cometary missions are of enormous fundamental importance for many different space science disciplines, including exobiology. Comets are presumed relics of the earliest, most primitive material in the solar nebula and are related to the planetesimals. They undoubtedly provided a general enrichment of volatiles to the inner solar system (contributing to atmospheres and oceans) and may have been key to the origin of life. A Discovery class, comet rendezvous mission, the Cometary Coma Chemical Composition (C4) Mission, was selected for further study by NASA earlier this year. The C4 Mission is a highly focused and usefully-limited subset of the Cometary Rendezvous Asteroid Flyby (CRAF) Mission, concentrating exclusively on measurements which will lead to an understanding of the chemical composition and make-up of the cometary nucleus. The scientific goals of the Cometary Coma Chemical Composition (C4) Mission are to rendezvous with a short-period comet and (1) to determine the elemental, chemical, and isotopic composition of the nucleus and (2) to characterize the chemical and isotopic nature of its atmosphere. Further, it is a goal to obtain preliminary data on the development of the coma (dust and gas composition) as a function of time and orbital position.

The Small Particles Intact Capture Experiment (SPICE) will develop technologies and engineering techniques necessary to capture nearly intact, uncontaminated cosmic and interplanetary dust particles (IDP's). Successful capture of such particles will benefit the exobiology and planetary science communities by providing particulate samples that may have survived unaltered since the formation of the solar system. Characterization of these particles may contribute fundamental data to our knowledge of how these particles could have formed into our planet Earth and, perhaps, contributed to the beginnings of life. The term 'uncontaminated' means that captured cosmic and IDP particles are free of organic contamination from the capture process and the term 'nearly intact capture' means that their chemical and elemental components are not materially altered during capture. The key to capturing cosmic and IDP particles that are organic-contamination free and nearly intact is the capture medium. Initial screening of capture media included organic foams, multiple thin foil layers, and aerogel (a silica gel); but, with the exception of aerogel, the requirements of no contamination or nearly intact capture were not met. To ensure no contamination of particles in the capture process, high-purity aerogel was chosen. High-purity aerogel results in high clarity (visual clearness), a useful quality in detection and recovery of embedded captured particles from the aerogel. P. Tsou at the Jet Propulsion Laboratory (JPL) originally described the use of aerogel for this purpose and reported laboratory test results. He has flown aerogel as a 'GAS-can Lid' payload on STS-47 and is evaluating the results. The Timeband Capture Cell Experiment (TICCE), a Eureca 1 experiment, is also flying aerogel and is scheduled for recovery in late April.

The Cassini Mission is a joint undertaking of NASA and the European Space Agency (ESA) to explore the Saturnian System with a Saturn Orbiter and a Titan Probe. The launch vehicle and the Saturn Orbiter are the responsibility of NASA while the Huygens Probe (detachable Titan Probe) is the responsibility of ESA. The spacecraft will be launched in 1996 and the Huygens Probe will arrive at Titan in 2003. The Cassini Mission-Huygens Probe provides a unique opportunity to obtain detailed information about the atmosphere and, possibly, the surface of Titan. Titan possesses a substantial nitrogen atmosphere containing methane and many other organic compounds. Aerosols play an important role in the atmospheric processes on Titan. The Huygens Probe offers an opportunity to determine how organic particles are formed and grow which will clarify their role on Earth. A powerful analytical instrument, capable of addressing the above technology and other science questions, was recently proposed for the Huygens Probe. It is comprised of an aerosol and gas sampler and processor, and a gas chromatograph-ion mobility spectrometer. The instrument will be able to measure complex organics that make up the collected aerosols to the approximate 1 ppm level. Gases will be measured to approximately 10 ppb. Because the Titan atmosphere is expected to be quite complex, a gas chromatograph-ion mobility spectrometer is used to provide unequivocal identification of the components of the analytes. Further details of the science question to be investigated and the proposed instrument are described. The expected results and their implications are also addressed.

In the gravitational field on earth, the large settling rate of micron-sized particles and the effects of gravity-induced convection prohibit many interesting studies of phenomena such as coagulation, collisions, and mutual interactions of droplets, dust grains and other particles. Examples of exobiology experiments involving these phenomena are the simulation of organic aerosol formation in Titan's atmosphere, studies of the role of comets in prebiotic chemical evolution, and simulations of carbon grain interactions in various astrophysical environments. The Gas-Grain Simulation Facility (GGSF) is a proposed earth-orbital laboratory that will allow present ground-based experimental programs which study processes involving small particles and weak interactions to be extended to a new domain. Physics issues that scientists wishing to propose GGSF experiments must consider are reviewed in this paper. Specifically, coagulation, motion in gases and vacua, and wall deposition of particles in a microgravity environment are discussed.

Instrumentation presently being developed by NASA for the collection and analysis of organic gases and aerosols in Titan's atmosphere is described together with the results of the preliminary experiments. For the aerosols, stepwise pyrolysis was shown to be a suitable method for preparing complex organic material for gas chromatography (GC), and a pyrolysis-gas chromatograph was developed and successfully used to analyze a simulated Titan aerosol. Atmospheric gases will be collected by a low-pressure gas sampling system using large-volume sample loops and analyzed by GC. The results of preliminary studies using a 20 cu cm sampling system and a very sensitive metastable ionization detector showed that hydrocarbon components at the 10 ppb level can be detected. Studies are in progress on shortening the overall analysis time by improving the pyrolysis system, the gas sampling system, and the associated gas chromatograph. Further development of the gas sampling system is planned to ensure rapid collection of samples adequate for analysis by GC over the entire range of pressures to be encountered during the probe's descent.

The National Aeronautics and Space Administration has begun preparations for the flight of the Mars Observer Mission in the early 1990s. An advanced ground-based study is being conducted on a usefully limited suite of Mars Soil Analog Materials (MarSAM) intended to simulate the aeolian material covering the surface of Mars. A series of variably proportioned iron/calcium smectite clays were prepared from a typical montmorillonite clay using the Banin method. The effect of increasing iron on a diverse set of chemical and spectroscopic properties of the suite of clays is discussed. In order to chemically characterize the MarSAM and compare them with the Martian soil studied by Viking, the clays were analyzed for their major and minor elemental compositions by X-ray fluorescence and ion-coupled plasma techniques. It was concluded that the surface iron has a complex and hitherto uninvestigated impact on the catalytic and spectroscopic properties of clays and on the ability of these material to store energy.

A detailed knowledge of the history and abundances of the biogenic elements and their compounds throughout the solar system can provide the exobiologists with a basis for understanding the conditions necessary for chemical evolution and the origin of life. The Ion Mobility Drift Spectrometer is an ion molecule reactor coupled with an ion drift spectrometer. Sample molecules are ionized to form product ions in the reactant region. An electric field moves the ions through a drift region against the flow of a drift gas where they are separated according to their size and structure producing an ion mobility spectrum. These spectra provide the IMDS with virtually universal sample identification capability. To conform to the rigid limits of weight, volume and consumables placed on flight instrumentation, several aspects of the IMDS must be studied and redesigned for flight use. In addition to miniaturization of the instrument, a reduction in the high flow rates used for the drift gas is an obvious necessary consideration. The effect of drastically reduced drift flow rates on IMDS spectra was investigated by lowering flow rates from 500ml/min to 50ml/min. Changes in peak shape, drift time and total spectra were studied at each flow rate.

Comets are some to the most primitive bodies in the solar system and therefore should contain elemental, chemical, and isotopic records of the early history of the solar system. An opportunity to perform in situ analyses of a comet nucleus exists with the Comet Rendezvous Asteroid Flyby (CRAF) mission. An integrated gas chromatograph/X-ray fluorescence instrument (MEDA), being proposed for inclusion onboard the CRAF spacecraft, will measure the molecular and elemental constituents of collected dust grains and ices. The gas chromatograph, employing helium ionization detectors and three columns designed to separate light gases, polar gases, and hydrocarbons will measure the volatile compounds of the biogenic elements thermally released from collected dust grains. The sensitivity of the GC for compounds of interest is at the picogram level. X-ray fluorescence utilized cryogenically cooled Si(Li) solid state detectors of nominal 150 eV resolution at 5.9 keV. Based on laboratory work with carbonaceous meteorites, both the GC and XRF can perform meaningful analyses with a few micrograms of collected comet dust.

In order to understand the origin and distribution of the biogenic elements and their compounds in the solar system, it will be necessary to study material from many classes of objects. Chemical, elemental, and isotopic measurements of returned samples of comets, asteroids, and possibly extra-solar system dust clouds would provide information on a particularly important class: the primitive objects. Extraterrestrial micron-sized particles in the vicinity of earth are one source of such materials that might otherwise be inaccessible. The Space Station appears to be an eminently suitable platform from which to collect and detect these various particles. The primary challenge, however, is to collect intact, uncontaminated particles which will be encounted at tens of kilometers per seconds. A concept for a micrometeoroid detector that could be deployed at a Space Station has been developed which uses a large area detector plate implanted with acoustic transducers. When an impact event occurs, the resulting signal is subjected to spectral analysis providing positive detection, momentum information, and angle of incidence. The primary advantage of this detector is the large area which increases the probability of measuring events.

Development of a gas chromatographic technique for analysis of aerosols and volatile organics from a Titan probe is now in progress. Preliminary investigations of aerosol collectors have shown that an electrostatic device should be the most efficient for the particle sizes expected in Titan's atmosphere. Such a device particularly lends itself to development of a simple pyrolyzer which can be used to break down any collected organic conglomerate structures into volatile fragments. Those fragments can subsequently be analyzed by GC providing information about the original chemical structure of the aerosols. Studies show that as little as 1 to 5 micrograms of model aerosol can be successfully analyzed. High altitude atmospheric gas sampling will also be important on Titan due to the great depth of the atmosphere. Studies show that a GC analysis of model Titan atmospheres at pressures approximating this altitude can be made with a sensitivity of a few ten's of parts-per-billion for the trace gases of interest.

Determination of molecular species comprised of the biogenic elements in the atmospheres of planets and moons of the solar system is one the foremost requirements of the exobiologist studying chemical evolution and the origin of life. Multiplex chromatography is a technique where many samples are pseudo-randomly introduced to the chromatograph without regard to elution of preceding components. The resulting data are then reduced using mathematical techniques such as cross correlation or Fourier Transforms. To demonstrate the utility of this technique for future solar system exploration, chemical modulators were developed. Several advantages were realized from this technique in combination with these modulators: improvement in detection limits of several orders of magnitude, improvement in the analysis of complex mixtures by selectively modulating some of the components present in the sample, increase in the number of analyses that can be conducted in a given period of time, and reduction in the amount of expendables needed to run an analysis. In order to apply this technique in a real application, methane in ambient air was monitored continuously over a period of one week. By using ambient air as its own carrier all expendables beyond power were eliminated.

The preliminary conceptual design for a cosmic dust collector is described. For the case of low Earth orbit (LEO), dust particles enter the collector through the collimator at a few volts negative potential due to charging in the ionosphere, at a velocity of 1 to 50 km/sec. The particles then pass through an electron stream and are charged to about 1 KV negative (regardless of incoming polarity). The 1 KV negatively charged particle then passes through three sensing grids coupled to charge sensitive preamps (CSP). The comparison of the two pulses provided by S(1) and S(2) are utilized by the microprocessor to determine the charge, q, on the particle (pulse amplitude) and its velocity, v (by time of flight). The third sensing grid, S(3), is kept at about 20 KV negative so that the dust particle will now be decelerated in passing from S(2) (zero potential) to S(3). S(3) is capacitively coupled to its CSP and the pulse from S(3) is utilized by the microprocessor to determine the particle's energy, E, and therefore its mass, m (again by time of flight) by comparison with the pulses from S(1) and S(2). The microprocessor can now precisely program the high-voltage switching network for the proper timing in the grounding of the successive deceleration grids. As determined by the microprocessor, each successive deceleration grid is grounded just after the dust particle passes, thus reducing the particle's energy by the amount q*100 KV at each stage. The microprocessor also determines at which stage the particle will fall below a certain critical energy where all remaining grids remain unswitched so that the particle will drift to the collector. The collector is kept at about 100V positive and is covered with gold foil to eliminate contamination and is removable for subsequent return to earth for detailed analysis.

The output current from a metastable ionization detector (MID) is applied to a modulation voltage circuit. An adjustment is made to balance out the background current, and an output current, above background, is applied to an input of a strip chart recorder. For low level concentrations, i.e., low detected output current, the ionization potential will be at a maximum and the metastable ionization detector will operate at its most sensitive level. When the detected current from the metastable ionization detector increases above a predetermined threshold level, a voltage control circuit is activated which turns on a high voltage transistor which acts to reduce the ionization potential. The ionization potential applied to the metastable ionization detector is then varied so as to maintain the detected signal level constant. The variation in ionization potential is now related to the concentration of the constituent and a representative amplitude is applied to another input of said strip chart recorder.

A multiplex gas chromatographic technique for the determination of methane in ambient air over extended periods is reported. A modest gas chromatograph which uses air as the carrier gas was modified by adding a silver oxide sample modulator for multiplex operation. The modulator selectively catalyzes the decomposition of methane in air. The resulting analytical system requires no consumables beyond power. A profile of the methane concentration in this laboratory was obtained for an 8-day period. During this period, methane concentration varied with an approximately daily period from a low of 1.53 + or - 0.60 ppm to a high of 4.63 + or - 0.59 ppm over the entire 8 days. Some of the measured concentrations are higher than those reported elsewhere indicating the presence of some local source or sources for methane. This work has demonstrated the utility of a relatively simple multiplex gas chromatograph for the analysis of environmental samples. The technique should be applicable to other trace components in air through use of other selective modulators.

Gas chromatography (GC) technology was developed for flight experiments in solar system exploration. The GC is a powerful analytical technique with simple devices separating individual components from complex mixtures to make very sensitive quantitative and qualitative measurements. It monitors samples containing mixtures of fixed gases and volatile organic molecules. The GC was used on the Viking mission in support of life detection experiments and on the Pioneer Venus Large Probe to determine the composition of the venusian atmosphere. A flight GC is under development to study the progress and extent of STS astronaut denitrogenation prior to extravehicular activity. Advanced flight GC concepts and systems for future solar system exploration are also studied. Studies include miniature ionization detectors and associated control systems capable of detecting from ppb up to 100% concentration levels. Further miniaturization is investigated using photolithography and controlled chemical etching in silicon wafers. Novel concepts such as ion mobility drift spectroscopy and multiplex gas chromatography are also developed for future flight experiments. These powerful analytical concepts and associated hardware are ideal for the monitoring of cabin atmospheres containing potentially dangerous volatile compounds.

The present investigation is concerned with a miniature metastable ionization detector featuring an unconventional electrode configuration, whose performance characteristics parallel those of traditional design. The ionization detector is to be incorporated in a flight gas chromatograph (GC) for use in the Space Shuttle. The design of the detector is discussed, taking into account studies which verified the sensitivity of the detector. The triaxial design of the detector is compared with a flat-plate style. The obtained results show that the principal goal of developing a miniature, highly sensitive ionization detector for flight applications was achieved. Improved fabrication techniques will utilize glass-to-metal seals and brazing procedures.

Inconsistencies and ambiguities are noted by the present consideration of Pioneer Venus and Venera atmospheric composition measurement of Venus in the context of lower atmosphere thermodynamic equilibrium. Among the scenarios projected on the basis of assumed correctness for selected data subsets, the O2 and SO2 concentrations reported by the Pioneer Venus chromatograph and the H2O concentrations reported by Venera 11 suggest that large concentrations of SO3 are present in the lower atmosphere of Venus. Such SO3 concentrations lead, however, to difficulties in explaining the atmosphere at and above the cloud tops, and in addition require specific assumptions concerning chemical reaction rates at and near the surface.

A gas chromatograph mounted in the Pioneer Venus sounder probe measured the chemical composition of the atmosphere of Venus at three altitudes. Ne, N2, O2, Ar, CO, H2O, SO2, and CO2 were measured, and upper limits set for H2, COS, H2S, CH4, Kr, N2O, C2H4, C2H6, and C3H8. Simulation studies have provided indirect evidence for sulfuric acid-like droplets and support the possibility of water vapor at altitudes of 42 and 24 km. The paper discusses the implications of these results for the origin, evolution, and present state of Venus' atmosphere.

Misidentification of two peaks from the Pioneer Venus sounder probe gas chromatograph (SPGC), also formerly known as the LGC, gave rise to quantitative errors in the abundances of oxygen, argon, and carbon monoxide. The argon abundance is estimated at 67 parts per million and that of carbon monoxide at 20 parts per million. At this time, no estimates for the oxygen abundance can be made.

The design logic, construction, function, and data processing of the Pioneer Venus Sounder Probe gas chromatograph instrument are discussed. A gas chromatograph for the analysis of the chemical composition of the lower atmosphere of Venus was included in the Sounder Probe of the Pioneer Venus mission. This paper describes the design logic of the gas chromatograph as constrained by the mission; attention is given to instrument construction, function, and data reduction.

The first gas chromatographic analysis of the lower atmosphere of Venus is reported. Three atmospheric samples were analyzed. The third of these samples showed carbon dioxide (96.4 percent), molecular nitrogen (3.41 percent), water vapor (0.135 percent), molecular oxygen (69.3 ppm), argon (18.6 ppm), neon (4.31 ppm), and sulfur dioxide (186 ppm). The amounts of water vapor and sulfur dioxide detected are roughly compatible with the requirements of greenhouse models of the high surface temperature of Venus. The large positive gradient of sulfur dioxide, molecular oxygen, and water vapor from the cloud tops to their bottoms, as implied by Earth-based observations and these results, gives added support for the presence of major quantities of aqueous sulfuric acid in the clouds. A comparison of the inventory of inert gases found in the atmospheres of Venus, Earth, and Mars suggests that these components are due to outgassing from the planetary interiors.

Earlier results reported from the Viking Lander-1 experiment are reexamined and interpreted in terms of a model of the Martian soil surface morphology and chemistry. Major events in the gas exchange experiment (GEX) first cycle are tabulated and data are presented on the sample processing and transport environments experienced by the soil samples. Oxygen and CO2 evolved from humidified Martian soil in GEX and slight changes in N2 present are investigated. A soil model involving iron oxide coating on silicate material is entertained to yield a mechanistic explanation of the experimental findings, and invocation of biotic processes is eschewed.

Gas chromatograph with sorbitol column, used in a three-part system, separates collected water from preconcentrated air samples.

Analyzer operates unattended or up to 15 hours. It has an automatic sample injection system and can be programmed. All fluid-flow valve switching is accomplished pneumatically from miniature three-way solenoid pilot valves.

Hydrogen, N, O, Kr methane and carbon dioxide gas chromatographic examination, discussing life detection device for Mars landing

Life detection for unmanned planetary exploration from extraterrestrial sample involving growth, gas changes and carbon dioxide fixation

Pyrolysis gas chromatography method for life detection and chemical identification of microorganisms

Soil moisture content was determined by extracting soil with methanol and subsequently analyzing the extract for water by gas chromatography. With air-dried mineral soils, this method gave slightly higher moisture content values than those obtained by the oven-dry method. Moisture content was determined quantitatively in soils to which various amounts of water had been added. The complete procedure, including extraction and analysis, requires less than one hour and gives results that closely compare to the oven-dry method.

To determine moisture content of soils rapidly and conveniently extract moisture with methanol and determine water content of methanol extract by gas chromatography. Moisture content of sample is calculated from weight of water and methanol in aliquot and weight of methanol added to sample.

Dual column ambient temperature system, consisting of pair of capillary columns, microbead thermistor detector and micro gas-sampling valve, is used in remote life-detection equipment for space experiments. Performance outweighs advantage gained by utilizing single-column systems to reduce weight, conserve carrier gas and operate at lower power levels.