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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.

Two alternative input sequences are commonly employed in correlation chromatography (CC). They are sequences derived according to the algorithm of the feedback shift register (i.e., pseudo random binary sequences (PRBS)) and sequences derived by using the uniform random binary sequences (URBS). These two sequences are compared. By applying the "cleaning" data processing technique to the correlograms that result from these sequences, we show that when the PRBS is used the S/N of the correlogram is much higher than the one resulting from using URBS.

The concept of a sample retention column that preserves the true time profile of an analyte of interest is studied. This storage system allows for the detection to be done at convenient times, as opposed to the nearly continuous monitoring that is required by other systems to preserve a sample time profile. The sample storage column is essentially a gas chromatography column, although its use is not the separation of sample components. The functions of the storage column are the selective isolation of the component of interest from the rest of the components present in the sample and the storage of this component as a function of time. Using octane as a test substance, the sample storage system was optimized with respect to such parameters as storage and readout temperature, flow rate through the storage column, column efficiency and storage time. A 3-h sample profile was collected and stored at 30 degrees C for 20 h. The profile was then retrieved, essentially intact, in 5 min at 130 degrees C.

Results are presented from a study in which a continuously changed gaseous sample was monitored by multiplex gas chromatography (MGC), using the exponential dilution (ED) technique of Ritter and Adams (1976) to change the composition and concentration of a gaseous mixture in such a way as to imitate changes in the atmospheric gases sampled by a descending aircraft. A calibration of the MGC system was performed with four different rates of sample dilution, and the errors resulting from various degrees of change in the sample concentration were determined.

Advanced microdevices for the exploration of the solar system have become increasingly important in the current environment of fiscal constraints and payload size limitations. The Discovery-class missions being proposed for future exploration, while being clearly responsive to this environment, will require highly miniaturized and efficient instruments based on these advanced devices. Several instrument concept developments are continuing at Ames Research Center in support of specific exobiology science goals in future solar system studies on candidate Discovery and other missions. Developments include highly miniaturized metastable ionization detectors for gas chromatography that weight as little as 1 - 2 grams with sensitivities of 10-14 mol/second and an advanced ion mobility spectrometer that has near-universal sensitivity and weighs as little as 200 grams. New chemical sensors based on solid-state pyroelectric devices are being studied and developed that weigh a few milligrams and, for example, have a sensitivity of 0.1 ppm for H2O2. Advanced X- ray diffraction and fluorescence instruments for crystallographic and geochemical measurements on unprepared soil and rock samples are under test. A stable isotope laser diode spectrometer for determination of 12C/13C and 18O/16O isotope ratios on Mars at fractional percent accuracies has been breadboarded. Finally, advanced computational methods are being applied to new instrument concepts allowing new, less complex, and thus, smaller instruments.© (1994) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.

Selective thermal modulation (STM) is a technique which produces a concentration-dependent pulse by selectively modulating a sample in a gas stream. Several types of modulation techniques, both chemical and physical, using adsorption, decomposition, and catalytic and mechanical methods have been developed for use with multiplex gas chromatography. Two of these applications involve selective modulation of the components present in the sample gas stream. The selective modulation of the concentration of specific sample molecules or classes of molecules provides additional analytical selectivity which can lead to selective detection. For some specific applications, the column may even be eliminated. Chemical modulation by absorption of a substance from the sample stream by a stationary phase will also produce a change in the signal intensity. Removal of a substance from the sample stream results in a signal containing a vacancy peak. In the work reported here, a selective thermal modulation technique has been developed as a method for determination of water vapor for possible use in Mars' atmosphere.

Important prebiotic organic compounds might have been transported to Earth in dust or produced in vapor clouds resulting from atmospheric explosions or impacts of comets. These compounds coalesced in the upper atmosphere with particles ejected from craters formed by impacts of large objects. Coalescence during exposure to UV radiation concentrated organic monomers and enhanced formation of oligomers. Continuing coalescence added material to the growing particles and shielded prebiotic compounds from prolonged UV radiation. These particles settled into the lower atmosphere where they were scavenged by rain. Aqueous chemistry and evaporation of raindrops containing nomomers in high temperature regions near the Earth's surface also promoted continued formation of oligomers. Finally, these oligomers were deposited in the oceans where continued prebiotic evolution led to the most primitive cell. Results of our studies suggest that prebiotic chemical evolution may be an inevitable consequence of impacting comets during the late accretion of planets anywhere in the universe if oceans remained on those planetary surfaces.

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 systems 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 +/- 0.60 ppm to a high of 4.63 +/- 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) is a powerful technique for analyzing gaseous mixtures. Applied to the earth's atmosphere, GC can be used to determine the permanent gases--such as carbon dioxide, nitrogen, and oxygen--and to analyze organic pollutants in air. The U.S. National Aeronautics and Space Administration (NASA) has used GC in spacecraft missions to Mars (the Viking Biology Gas Exchange Experiment [GEX] and the Viking Gas Chromatograph-Mass Spectrometer [GC-MS]) and to Venus (the Pioneer Venus Gas Chromatograph [PVGC] on board the Pioneer Venus sounder probe) for determining the atmospheric constituents of these two planets. Even though conventional GC was very useful in the Viking and Pioneer missions, spacecraft constraints and limitations intrinsic to the technique prevented the collection of more samples. With the Venus probe, for instance, each measurement took a relatively long time to complete (10 min), and successive samples could not be introduced until the previous samples had left the column. Therefore, while the probe descended through the Venusian atmosphere, only three samples were acquired at widely separated altitudes. With the Viking mission, the sampling rate was not a serious problem because samples were acquired over a period of one year. However, the detection limit was a major disadvantage. The GC-MS could not detect simple hydrocarbons and simple alcohols below 0.1 ppm, and the GEX could not detect them below 1 ppm. For more complex molecules, the detection limits were at the parts-per-billion level for both instruments. Finally, in both the Viking and Pioneer missions, the relatively slow rate of data acquisition limited the number of analyses, and consequently, the amount of information returned. Similar constraints are expected in future NASA missions. For instance, gas chromatographic instrumentation is being developed to collect and analyze organic gases and aerosols in the atmosphere of Titan (one of Saturn's satellites). The Titan-Cassini entry probe, which is being jointly planned by NASA and the European Space Agency (ESA), might be launched as early as 1994. As in the Pioneer mission, limited time--perhaps only 3-4 h--will be available for the completion of all analyses while the probe descends through the atmosphere. A conventional GC or GC-MS system would be able to analyze no more than two aerosol and two gas samples during the probe's descent. Conventional GC also is limited by the sensitivity of the detector and by the sample volume. For the Titan mission, the sensitivity problems will be worse because the atmospheric pressure at the time of instrument deployment is expected to be3 torr. Consequently, the sample volume might not be large enough to satisfy the detector sensitivity requirements. Because of such limitations, alternative GC analysis techniques have been investigated for future NASA missions. Multiplex gas chromatography has been investigated as a possible candidate for chemical analysis within a spacecraft or other restricted environment, and chemical modulators have been developed and used when needed with this technique to reduce the size and weight of the instrumentation. Also, several new multiplex techniques have been developed for use in specific applications.

We report a new technique for measurement of the spatial growth rate of a Stokes pulse in liquids generated by a single picosecond laser pulse. Solutions to the coupled differential equations describing the Stokes growth, taken in the region where the depletion of the laser pulse is small, show that the Stokes pulse grows exponentially with a rate equal to gsIl. Experiments performed in ethanol where gs, the Stokes gain, is known allows us to calculate the initial laser intensity, Il. This technique shows promise as a convenient method for measuring the absolute intensity of picosecond laser pulses.

During the next decade or so, NASA, in conjunction with the European Space Agency, plans to send a spacecraft to the Saturnian system so that local studies of Saturn and its satellite, Titan, can be made. In order to study the atmosphere of Titan, analysis of both aerosols and gases will have to be made. To accomplish this, gas chromatographic instrumentation for the collection and analysis of organic gases and aerosols in Titan's atmosphere is being developed. The aerosols will be collected and then subjected to pyrolysis-gas chromatography. Results using a simple pyrolysis-GC system and tholin, made by subjecting a nominal Titan mixture (96.8% N2, 3% CH4, 0.2% H2) to laser-supported shocks, show that many compounds, including hydrocarbons and simple nitriles, can be identified by this technique. Atmospheric gases will be collected using large volume (10 cm3) sample loops and then analyzed by gas chromatography. Large volume samples are required because the ambient pressures, where the probe instruments are first deployed, will be low (10 mbar). Preliminary studies using a 20 cm3 sampling system and a very sensitive meta-stable ionization detector show that hydrocarbon components at the 10 ppb level can be detected. Work will continue to improve GC sensitivity, minimize analysis time, and develop interfaces with suitable sample collectors for analysis of atmospheres by future spacecraft.

Dans la technique decrite, la decomposition thermique est utilisee a l'entree de la colonne pour creer des impulsions de concentration dans un echantillon en ecoulement continu pour l'analyse chromatographique avec multiplexage. Le chromatogramme obtenu contient des lacunes